IMPROVEMENTS IN AND RELATING TO ION ANALYSIS

Abstract

A method of processing an image-charge/current signal representative of one or more ions undergoing oscillatory motion within an ion analyser apparatus, the method comprising obtaining a recording of the image-charge/current signal generated by the ion analyser apparatus in the time domain. By a signal processing unit, the method includes selecting N (where N is an integer>1) separate values (OP.sub.n, where n=1 to N; N?M) of the frequency-domain spectrum of the image-charge/current signal each from amongst a plurality of spectral peaks which include a harmonic peak associated with a target ion. By solving a system of equations:

[00001]${\mathrm{OP}}_n=\underset{m=1}{\overset{N}{.Math.}}{?}_{nm}?{\mathrm{TP}}_m,$$\mathrm{for}n=1\mathrm{to}N;$$N?M$ where ?.sub.nm are coefficients and TP.sub.m are corrected values of the spectrum, the charge of the target ion is determined based on a magnitude of a corrected value(s) (TP.sub.m) associated with that ion.

Claims

1. A method of processing an image-charge/current signal representative of one or more ions undergoing oscillatory motion within an ion analyser apparatus, the method comprising: obtaining a recording of the image-charge/current signal generated by the ion analyser apparatus in the time domain; by a signal processing unit: applying a transform of the recorded signal to provide a frequency-domain signal; selecting N (where N is an integer>1) separate values (OP.sub.n, where n=1 to N; N?M) of the frequency-domain signal each from amongst a plurality of separate adjacent signal peaks of the frequency-domain signal which include a signal peak corresponding to a target ion; and, solving a system of equations: ${\mathrm{OP}}_n=\underset{m=1}{\overset{M}{.Math.}}{?}_{nm}?{\mathrm{TP}}_m,\mathrm{for}n=1\mathrm{to}N;N?M$ where ?.sub.nm are coefficients and TP.sub.m are corrected values of M of the selected N separate values of the frequency-domain signal; selecting the corrected value (TP.sub.m) from amongst the M corrected values of the frequency-domain signal corresponding to a signal peak (e.g. a harmonic peak) associated with the target ion; calculating a value representative of the charge of said target ion undergoing oscillatory motion within the ion analyser apparatus based on the selected corrected value (TP.sub.m).

2. A method according to claim 1 wherein at least one of the selected N separate values of the frequency-domain signal corresponds to a respective adjacent signal peak which resides at a frequency that is not a harmonic frequency of target ion.

3. A method according to claim 1 wherein, before said step of applying a transform of the recorded signal to provide a frequency-domain signal: determining a value for the period of a periodic signal component within the recorded signal; truncating the recorded signal to provide a truncated signal having a duration substantially equal to an integer multiple of said period; and subsequently, performing said step of applying a transform of the recorded signal in which the recorded signal is the truncated signal, to provide said frequency-domain signal; whereby, said step of calculating a value representative of the charge of a said target ion is based on a corrected value (TP.sub.m) of the frequency-domain signal corresponding to the truncated signal.

4. A method according to claim 3 wherein the duration of the truncated signal is an integer multiple of the period of the target ion oscillation.

5. A method according to claim 3 wherein the truncated signal is a sub-portion of the recorded signal which starts at a recorded time after the recorded start time of the recorded image-charge/current signal and ends at a recorded time before the recorded end time of the recorded image-charge/current signal.

6. A method according to claim 3 wherein the truncated signal is a sub-portion of the recorded signal within which a sequence of repeating signal peaks reside which each have a respective peak signal value which deviates by not more than about 20% from the value of the largest peak value amongst the sequence of repeating signal peaks.

7. A method according to claim 3 wherein said truncating the recorded signal comprises: transforming the recorded time-domain signal in to a frequency-domain thereby to generate a transformed recorded signal; selecting a peak value of the transformed recorded signal from within a signal peak of the transformed recorded signal corresponding to a frequency-domain harmonic component of the recorded signal; selecting a first adjacent value of the transformed recorded signal within the signal peak and corresponding to a frequency less than the frequency associated with the peak value; selecting a second adjacent value of the transformed recorded signal within the signal peak and corresponding to a frequency greater than the frequency associated with the peak value; reconstructing a time-domain signal based on the selected peak value, the selected first adjacent value and the selected second adjacent value; determining a threshold time at which an amplitude modulation within the reconstructing a time-domain signal falls below a threshold signal value; truncating the recorded signal according to the threshold time so determined.

8. A method according to claim 7 wherein said threshold signal value is a signal value corresponding about 80% of the largest value of the amplitude modulation.

9. A method according to claim 7 wherein the frequency associated with the selected peak value is substantially equal to the frequency of the harmonic associated with the given signal peak of the transformed recorded signal.

10. A method according to claim 7 wherein the selected peak value, the selected first adjacent value and the selected second adjacent value are obtained from the spectral peak corresponding to the N.sup.th harmonic of the frequency-domain harmonic components of the recorded signal, wherein N is an integer greater than one (1).

11. A method according to claim 10 wherein N=3 (three).

12. A method according to claim 7 wherein the first adjacent value is selected to correspond to a frequency that is lower than the frequency of the selected peak value by an amount not exceeding half of the full-width-at-half-maximum (FWHM) of the given signal peak of the transformed recorded signal.

13. A method according to claim 7 wherein the second adjacent value is selected to correspond to a frequency that is higher than the frequency of the selected peak value by an amount not exceeding half of the full-width-at-half-maximum (FWHM) of the given signal peak of the transformed recorded signal.

14. A method according to claim 12 wherein the first adjacent value and the second adjacent value are each selected to correspond to a respective frequency that differs from the frequency of the selected peak value by the same amount.

15. A method according to claim 1 wherein the step of reconstructing a time-domain signal based on a selected one or more frequency-domain harmonic components of the truncated signal, comprises calculating a time-domain signal using an inverse transform of the frequency-domain transform applied to the truncated time domain signal to generate said frequency-domain harmonic components of the truncated signal.

16. A method according to claim 1 wherein said value representative of the charge of a said ion is proportional to said selected corrected value (TP.sub.m).

17. A method according to claim 1 wherein the step of obtaining a recording of the image-charge/current signal generated by the ion analyser apparatus in the time domain includes obtaining a plurality of image charge/current signals before processing the plurality of image charge/current signals by said signal processing unit, wherein obtaining the plurality of image charge/current signals includes: producing ions; trapping the ions such that the trapped ions undergo oscillatory motion; and obtaining a plurality of image charge/current signals representative of the trapped ions undergoing oscillatory motion using at least one image charge/current detector.

18. An ion analyser apparatus configured to generate an image charge/current signal representative of one or more ions undergoing oscillatory motion therein, wherein the ion analyser apparatus is configured to implement the method according to claim 1.

19. An ion analyser apparatus according to claim 18 comprising any one or more of: an ion cyclotron resonance trap; an Orbitrap? configured to use a hyper-logarithmic electric field for ion trapping; an electrostatic linear ion trap (ELIT); a quadrupole ion trap; an ion mobility analyser; a charge detection mass spectrometer (CDMS); Electrostatic Ion Beam Trap (EIBT); a Planar Orbital Frequency Analyser (POFA); or a Planar Electrostatic Ion Trap (PEIT), for generating said oscillatory motion therein.

20. An ion analyser apparatus configured for generating an image-charge/current signal representative of oscillatory motion of one or more ions received therein, the apparatus comprising: an ion analysis chamber configured for receiving said one or more ions and for generating said image charge/current signal in response to said oscillatory motion; a signal recording unit configured for recording the image charge/current signal as a recorded signal in the time domain; a signal processing unit for processing the recorded signal to: apply a transform of the recorded signal to provide a frequency-domain signal; select N (where N is an integer>1) separate values (OP.sub.n, where n=1 to N; N?M) of the frequency-domain signal each from amongst a plurality of separate adjacent signal peaks of the frequency-domain signal which include a signal peak corresponding to a target ion; and, solving a system of equations: ${\mathrm{OP}}_n=\underset{m=1}{\overset{M}{.Math.}}{?}_{nm}?{\mathrm{TP}}_m,\mathrm{for}n=1\mathrm{to}N;N?M$ where ?.sub.nm are coefficients and TP.sub.m are corrected values of M of the selected N separate values of the frequency-domain signal; select the corrected value (TP.sub.m) from amongst the M corrected values of the frequency-domain signal corresponding to a signal peak (e.g. a harmonic peak) associated with the target ion; calculate a value representative of the charge of said target ion undergoing oscillatory motion within the ion analyser apparatus based on the selected corrected value, (TP.sub.m).

21. An ion analyser apparatus according to claim 20 wherein at least one of the selected N separate values of the frequency-domain signal corresponds to a respective adjacent signal peak which resides at a frequency that is not a harmonic frequency of target ion.

22. An ion analyser apparatus according to claim 20 wherein the signal processing unit is configured for processing the recorded signal to: determine a value for the period of a periodic signal component within the recorded signal; truncate the recorded signal to provide a truncated signal having a duration substantially equal to an integer multiple of said period; perform said step of applying a transform of the recorded signal in which the recorded signal is the truncated signal, to provide said frequency-domain signal; whereby, said step of calculating a value representative of the charge of a said target ion is based on a corrected value (TP.sub.m) of the frequency-domain signal corresponding to the truncated signal.

23. An ion analyser apparatus according to claim 20 wherein the ion analyser apparatus is configured for producing ions, and the ion analysis chamber is configured for; trapping the ions such that the trapped ions undergo oscillatory motion; and obtaining a plurality of image charge/current signals representative of the trapped ions undergoing oscillatory motion using at least one image charge/current detector

24. An ion analyser apparatus according to claim 20 comprising any one or more of: an ion cyclotron resonance trap; an Orbitrap? configured to use a hyper-logarithmic electric field for ion trapping; an electrostatic linear ion trap (ELIT); a quadrupole ion trap; an ion mobility analyser; a charge detection mass spectrometer (CDMS); Electrostatic Ion Beam Trap (EIBT); a Planar Orbital Frequency Analyser (POFA); or a Planar Electrostatic Ion Trap (PEIT), for generating said oscillatory motion therein.

25. A computer-readable medium having computer-executable instructions configured to cause a mass spectrometry apparatus to perform a method of processing a plurality of image charge/current signals representative of trapped ions undergoing oscillatory motion, the method being according to claim 1.

Description

SUMMARY OF THE FIGURES

[0088] Embodiments and experiments illustrating the principles of the invention will now be discussed with reference to the accompanying figures in which:

[0089] FIG. 1a shows the theoretical form of a STORI plots according to the prior art;

[0090] FIG. 1b shows several STORI plots according to a simulation;

[0091] FIG. 2a shows an ion analyser apparatus according to an embodiment of the invention;

[0092] FIG. 2b shows an image-charge/current signal generated by an ion analyser apparatus comprising a plurality of pulses within the image-charge/current signal forming a periodic succession of repetitive signal pulses, with repetition period T;

[0093] FIG. 2c shows a schematic representation of a 2D function comprising a stack of segmented portions of an image-charge/current signal representative of oscillatory motion of one or more ions in an ion analyser apparatus;

[0094] FIG. 2d shows a schematic representation of an image-charge/current signal such as shown in FIG. 2c, in which a process of segmentation is being applied;

[0095] FIGS. 2e and 2f show an image-charge/current signal generated by an ion analyser apparatus corresponding to FIG. 2a, comprising a plurality portions of duration T (seconds) of the same one image-charge/current signal that contains a periodic succession of repetitive signal pulses, with repetition period T. Each of the portions is overlaid upon each other, so as to be co-registered with each other upon the same time axis section (t=0 to t=T), in the view of FIG. 2b. Each of the portions is stacked along a dimension perpendicular to the time axis in alignment so as to be co-registered with each other in the view of FIG. 2c;

[0096] FIG. 3 shows a frequency spectrum of a recorded image-charge/current signal that contains a succession of spectral peaks located at frequency harmonics;

[0097] FIG. 4 shows an image-charge/current signal reconstructed using three values selected from within the third harmonic (H3) peak in the frequency spectrum of FIG. 3, and from the reconstructed signal an estimate of the lifetime of the ion responsible for the original signal;

[0098] FIG. 5 shows an image-charge/current signal to be truncated based on an estimate of the lifetime of the ion shown in FIG. 4;

[0099] FIG. 6 shows a frequency spectrum of a truncated recorded image-charge/current signal that has been truncated as indicated in FIG. 5 and which contains a succession of spectral peaks located at frequency harmonics;

[0100] FIG. 7 shows an image-charge/current signal reconstructed using values selected from within multiple spectral peaks located at frequency harmonics (H1, H2, H3) in the frequency spectrum of FIG. 6, and which contains a periodic succession of repetitive signal pulses, with repetition period T. Also shown is the original (non-reconstructed) image-charge/current signal from which the reconstructed signal derives;

[0101] FIG. 8 shows a frequency spectrum of a recorded image-charge/current signal that contains a succession of spectral peaks located at frequency harmonics (H1, . . . , Hi) generated by oscillatory motion of a target ion, and each of which is surrounded by a number of smaller adjacent harmonic spectral peaks generated by oscillatory motion of other non-target ions;

[0102] FIG. 9 shows a section of a frequency spectrum of a recorded image-charge/current signal that contains cluster of three spectral peaks located at frequency harmonics from amongst a succession (not shown) of further spectral spectral peaks generated by oscillatory motion of a target ion. The cluster contains a main (target) harmonic spectral peak peak and two smaller adjacent spectral peaks located at frequency harmonics generated by oscillatory motion of other non-target ions. Also shown is a system of three simultaneous equations associated with the three spectral peaks;

[0103] FIG. 10 shows a method according to an embodiment of the invention, which may be implemented on an ion analyser apparatus according to FIG. 2a;

[0104] FIG. 11 shows a schematic view of a recorded image-charge/current signal of full duration TR, comprised of a pure sine wave oscillatory signal of lifetime LT;

[0105] FIG. 12 shows a schematic view of frequency bins in the Fourier spectrum of the recorded image-charge/current signal both before and after its truncation;

[0106] FIG. 13 shows a schematic view of three different recorded image-charge/current signals of differing duration associated with different ions;

[0107] FIG. 14 shows a true recorded image-charge/current signal.

DETAILED DESCRIPTION OF THE INVENTION

[0108] Aspects and embodiments of the present invention will now be discussed with reference to the accompanying figures. Further aspects and embodiments will be apparent to those skilled in the art. All documents mentioned in this text are incorporated herein by reference.

[0109] The features disclosed in the foregoing description, or in the following claims, or in the accompanying drawings, expressed in their specific forms or in terms of a means for performing the disclosed function, or a method or process for obtaining the disclosed results, as appropriate, may, separately, or in any combination of such features, be utilised for realising the invention in diverse forms thereof.

[0110] While the invention has been described in conjunction with the exemplary embodiments described above, many equivalent modifications and variations will be apparent to those skilled in the art when given this disclosure. Accordingly, the exemplary embodiments of the invention set forth above are considered to be illustrative and not limiting. Various changes to the described embodiments may be made without departing from the spirit and scope of the invention.

[0111] For the avoidance of any doubt, any theoretical explanations provided herein are provided for the purposes of improving the understanding of a reader. The inventors do not wish to be bound by any of these theoretical explanations.

[0112] Any section headings used herein are for organizational purposes only and are not to be construed as limiting the subject matter described.

[0113] Throughout this specification, including the claims which follow, unless the context requires otherwise, the word comprise and include, and variations such as comprises, comprising, and including will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

[0114] It must be noted that, as used in the specification and the appended claims, the singular forms a, an, and the include plural referents unless the context clearly dictates otherwise. Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by the use of the antecedent about, it will be understood that the particular value forms another embodiment. The term about in relation to a numerical value is optional and means for example+/?10%.

[0115] In the drawings, like items are assigned like reference symbols, for consistency.

[0116] FIG. 2a shows a schematic representation of an ion analyser apparatus in the form of an electrostatic ion trap 80 for mass analysis. The electrostatic ion trap includes an ion analysis chamber (81, 82, 83, 84) configured for receiving one or more ions 85A and for generating an image charge/current signal in response to oscillatory motion 86B of the received ions 85B when within the ion analysis chamber. The ion analysis chamber comprises a first array of electrodes 81 and a second array of electrodes 82, spaced from the first array of electrodes by a substantially constant separation distance.

[0117] A voltage supply unit (not shown) is arranged to supply voltages, in use, to electrodes of the first and second arrays of electrodes to create an electrostatic field in the space between the electrode arrays. The electrodes of the first array and the electrodes of the second array are supplied, from the voltage supply unit, with substantially the same pattern of voltage, whereby the distribution of electrical potential in the space between the first and second electrode arrays (81, 82) is such as to reflect ions 85B in a flight direction 86B causing them to undergo periodic, oscillatory motion in that space. The electrostatic ion trap 80 may be configured, for example, as is described in WO2012/116765 (A1) (Ding et al.), the entirety of which is incorporated herein by reference. Other arrangements are possible, as will be readily appreciated by the skilled person.

[0118] The periodic, oscillatory motion of ions 85B within the space between the first and second arrays of electrodes may be arranged, by application of appropriate voltages to the first and second arrays of electrodes, to be focused substantially mid-way between the first and second electrode arrays for example, as is describe in WO2012/116765 (A1) (Ding et al.). Other arrangements are possible, as will be readily appreciated by the skilled person.

[0119] One or more electrodes of each of the first and second arrays of electrodes, are configured as image-charge/current sensing electrodes 87 and, as such, are connected to a signal recording unit 89 which is configured for receiving an image-charge/current signal 88 from the sensing electrodes, and for recording the received image charge/current signal in the time domain. The signal recording unit 89 may comprise amplifier circuitry as appropriate for detection of an image-charge/current having periodic/frequency components related to the mass-to-charge ratio of the ions 85B undergoing said periodic oscillatory motion 86B in the space between the first and second arrays of electrodes (81, 82).

[0120] The first and second arrays of electrodes may comprise, for example, planar arrays formed by: [0121] (a) parallel strip electrodes; and/or, [0122] (b) concentric, circular, or part-circular electrically conductive rings,
as is described in WO2012/116765 (A1) (Ding et al.). Other arrangements are possible, as will be readily appreciated by the skilled person. Each array of the first and second arrays of electrodes extends in a direction of the periodic oscillatory motion 86B of the ion(s) 85B. The ion analysis chamber comprises a main part defined by the first and second arrays of electrodes and the space between them, and two end electrodes (83, 84). A voltage difference applied between the main segment and the respective end segments creates a potential barrier for reflecting ions 85B in the oscillatory motion direction 86B, thereby to trap the ions within the space between the first and second arrays of electrodes. The electrostatic ion trap may include an ion source (not shown, e.g. an ion trap) configured for temporarily storing ions 85A externally from the ion analysis chamber, and then injecting stored ions 80A into the space between the first and second arrays of electrodes, via an ion injection aperture formed in one 83 of the two end electrodes (83, 84). For example, the ion source may include a pulser (not shown) for injecting ions into the space between the first and second arrays of electrodes, as is described in WO2012/116765 (A1) (Ding et al.). Other arrangements are possible, as will be readily appreciated by the skilled person.

[0123] The ion analyser 80 further incudes a signal processing unit 91 configured for receiving a recorded image-charge/current signal 90 from the signal recording unit 89, and for processing the recorded signal to: [0124] (a) Apply a transform of the recorded signal to provide a frequency-domain signal; [0125] (b) Select N (where N is an integer>1) separate values (OP.sub.n, where n=1 to N; N?M) of the frequency-domain signal each from amongst a plurality of separate adjacent signal peaks of the frequency-domain signal which include a signal peak (e.g. a harmonic peak) corresponding to a target ion; and, solving a system of equations:

[00016]${\mathrm{OP}}_n=\underset{m=1}{\overset{M}{.Math.}}{?}_{\mathrm{nm}}?{\mathrm{TP}}_m,\mathrm{for}n=1\mathrm{to}N;N?M$ [0126] where ?.sub.nm are coefficients and TP.sub.m are corrected values of M of the selected N separate values of the frequency-domain signal; [0127] (c) Select a corrected value (TP.sub.m) for the frequency-domain signal corresponding to a harmonic peak associated with the target ion; [0128] (d) Calculate a value representative of the charge of the target ion undergoing oscillatory motion within the ion analyser apparatus based on the selected corrected value (TP.sub.m).

[0129] The value representative of the charge of the target ion may be, for example, the value of the selected corrected value (TP.sub.m) for the frequency-domain peak after multiplication by a normalisation or calibration constant or term according normalisation/calibration procedures readily apparent to the skilled person which characterise the proportionality relationship between TP.sub.m and the corresponding ion charge, q, in terms of the weighting field as described above. Often, there are ions present in the ion analyser device used to generate the image-charge/current signal, and these other ions undergo oscillatory motion at different respective oscillation frequencies and corresponding periods (F.sub.other=1/T.sub.other). These co-exist in the ion analyser and their respective oscillation frequencies may be quite close to the oscillation frequency of the target ion. These other signals present spectral peaks in the frequency spectrum of the time-domain signal that do not present as similar spectral peaks (e.g. not similar to delta functions)they are generally smaller in amplitude and wider in width. As a result of this, the foot, base or tail of these other peaks may spread to frequencies associated with the oscillatory motion of the target ion and in so doing may interfere with the height and/or position of the sharp, tall spectral peaks associated with the target ion.

[0130] As will be described in more detail below, the present method implements steps to reduce/eliminate the interferences from the nearby peaks. By nearby, it is meant that these peaks fall into the predetermined range (?F, selected by the user: e.g. 0<?F<F.sub.0, where F.sub.0 is the fundamental frequency of the ion oscillation, such that the range ?F excludes neighbouring harmonics of that oscillation) of the targeted frequency. A system of simultaneous equations for the multiple components of nearby frequencies is established and the solution to that system of equations is used to calculate the contribution from the other ions oscillating frequencies resulting in spectral components near to the targeted frequency of the target ion. These contributions are deducted from the spectrum of the signal, and the remaining targeted frequency component is used to calculate the charge of the targeted ion.

[0131] Interferences may be eliminated within the context of the more general methods of the invention illustrated with reference to FIG. 10 as follows, for example, within step (E) below: [0132] (A) Obtain a recorded image-charge/current charge signal (FIG. 10, Step S1): [0133] (B) Detect a set of periodic/repeating pulses in the recorded image-charge/current charge signal, and for that detected set of periodic/repeating pulses determine a period (T) for the set of periodic/repeating pulses (FIG. 10, Step S2); [0134] (C) Determine an estimate of the lifetime of the detected set of periodic/repeating pulses; [0135] (D) Adjust/truncate the length of the recorded image-charge/current charge signal containing the detected set of periodic/repeating pulses to be less than (and within) the determined lifetime, and so that the duration of the signal is an integer multiple of the period of the periodic/repeating pulses, and apply a frequency transform (e.g. Fourier transform) to the signal (FIG. 10, Step S3, S4); [0136] (E) Obtain amplitudes or magnitudes of the transformed signal at the target frequency (F=1/T) and its higher harmonics; and, [0137] a. Find other peaks in a predetermined range near the targeted frequency and their harmonics, and determine their contribution at the targeted frequency and its harmonics; [0138] b. Adjust the amplitudes or magnitudes of a plurality (e.g. up to 12 or more) harmonics of the targeted frequency by deducting the contribution of the interferences from the nearby frequency peaks in accordance with solving the system of N equations described above; [0139] (F) Use real and imaginary spectral values of one or more of those harmonics to calculate a charge value of the target ion (FIG. 10, Step S5).

[0140] As one example of implementing step (D), above, FIGS. 2e and 2f show the experimentally acquired time-domain image-charge/current signal which was segmented by the signal period and stacked together to form a F.sub.2(t.sub.1, t.sub.2) plot described in detail below with reference to FIG. 2c. By removing the points above the threshold (Threshold C) the 2D plot clearly shows that the signal disappeared near t.sub.2=500 ms (i.e. the lifetime of ion. See FIG. 5: T.sub.Life). Therefore, the processing of the image-charge/current signal for this particular ion event should only focus to this lifetime (i.e. t.sub.2<500 ms). Now with reference to FIG. 5, the method truncates the time-domain image-charge/current signal to just slightly shorter than T.sub.Life so that the length of signal equals an integer multiple of the period (T) of this targeted ion motion.

[0141] For the frequency-transformed spectrum of an image-charge/current signal comprising a normal non-harmonic waveform, the number of high order harmonic spectral components (Hi) up to 12 (i.e. i=12) would be sufficient, and for a practical image-charge/current signal acquired by practical detector, and signal amplifier with limited band width, the number of order up to 5 or even 4 (i.e. i=4 to 5) would be sufficient and this can efficiently eliminate the contribution from noise and interferences. Using the cleaned spectrum that contains only a few lines, one can, if desired, also reconstruct the time domain signal.

[0142] However, when there are other ions having similar frequencies around the targeted frequency, their frequency peaks may still influence the values at the targeted frequency, as well as its high harmonics. This is important when one wishes to run many ions in one trap cycle to increase the throughput of the measurement. When hundreds of ions fly together, it is likely that some ions fall into the frequency range that is close to the targeted frequency. The other frequency peaks cannot be represented by sharp spectral peaks (e.g. delta functions) because the signal truncation was not aligned with those other frequencies. The leakage of such nearby peaks will result in significant interferences with the targeted frequency.

[0143] FIG. 8 shows an example of such interference, where the targeted frequency H1 and its higher harmonic Hi, both are represented by delta functions, are surrounded by two other frequencies 12, 13. These two peaks have some side lobes 14 (or frequency leakage) that will extend to the targeted frequency (H1) and to each other. It is preferable to identify such contribution from the nearby frequencies and to remove the contribution before target ion charge measurement. The present method thus includes such a correction step, as noted above, and described in detail below. In the correction step a number of interfering frequencies are identified within a predetermined frequency range, selected by the user, around the targeted frequency and their interference is removed.

[0144] In the frequency spectrum (as in FIG. 8) the observed peak value is actually the weighted combination of all components (in terms of their true peak values). Based on the known signal length used for the frequency (e.g. Fourier) transform, it has been found that a mathematical description of the distribution (weights/coefficients) for each frequency component can be derived. It has been found that a matrix of coupled equations can be constructed for sums of the contributions from all components (true peak value multiplied by a weight/coefficient) that are equal to the observed peak values. The inventors have found that a solution to this system of coupled equations gives true peak value at the targeted frequency.

[0145] By removal of the nearby frequency interferences to the targeted frequency (including interferences to the higher harmonics of the targeted frequency), reconstruction of the targeted frequency signal can be much more accurate even if there are many ions of different frequencies were flying together and their signal are co-acquired. Further filtering or smoothing of the reconstructed time domain signal may also be used before measuring its magnitude, and this can be added as general steps of signal processing as would be readily available within the common knowledge of signal processing.

[0146] In the method, the step of selecting one or more values of the frequency-domain signal comprises selecting N (where N is an integer>1) separate values (OP.sub.n, where n=1 to N; N?M) of the frequency-domain signal each from amongst a plurality of separate adjacent signal peaks of the frequency-domain signal which include a signal peak corresponding to a target ion; and, solving a system of N equations:

[00017]${\mathrm{OP}}_n=\underset{m=1}{\overset{M}{.Math.}}{?}_{\mathrm{nm}}?{\mathrm{TP}}_m,\mathrm{for}n=1\mathrm{to}N;N?M$

where ?.sub.nm are coefficients and TP.sub.m are corrected values of M of the selected N separate values of the frequency-domain signal. Then, the method proceeds by selecting a corrected value (TP.sub.m) for the value of the frequency-domain signal corresponding to a harmonic peak associated with the target ion. At least one of the selected N separate values of the frequency-domain signal corresponds to a respective adjacent signal peak which resides at a frequency that is not a harmonic frequency of target ion.

[0147] That is to say, amongst the selected N separate values of the frequency-domain signal are values that correspond to a respective adjacent signal peak (e.g. FIG. 9: peak #2, peak #3) which resides at a frequency that is not a harmonic frequency of the target ion (i.e. peak #1, the ion we wish to determine the charge of). For example, OP.sub.1 may a value of the frequency-domain signal from within peak #1 corresponding to a frequency which is a harmonic of the motion of the target ion. This may be the value observed to be the highest value within the signal peak #1 shape corresponding to a harmonic. Similarly, OP.sub.n (where n>1) may be values of the frequency-domain signal peaks #2 and #3 etc., corresponding respectively to a frequency which is a harmonic of the motion of another respective ion (i.e. N?1 other ions in total) that is not the target ion. Again, these adjacent peak values may each be a value observed to be the highest value within the signal peak shape corresponding to a harmonic.

[0148] With these N selected values of the frequency-domain signal (N=3 in FIG. 9) a set of equations is generated which represents the contributions (?.sub.nm) made to each one of the selected separate values (OP.sub.n) of the frequency-domain signal, by the motion of all ions contributing to the signal associated with a given harmonic of the target ion.

[0149] The method includes solving this set of equations, one may obtain a corrected (i.e. true) value (TP.sub.1) of the frequency-domain signal associated with a given harmonic of the target ion for which the spectral energy arising from the motion of the all other ions contributing to the signal at that frequency, is removed. The method also obtains a corrected (true) value TP.sub.n (where n>1) of the frequency-domain signal associated with the adjacent harmonics of the non-target ion(s). These are the other ions which contribution spectral energy to the harmonic of the target ion.

[0150] In the example of FIG. 9, three separate values of the frequency-domain signal are selected, each corresponding to a respective one of three (N=3) signal peaks (peaks #1, #2 and #3). Each of these three peaks resides at a respective frequency that is a harmonic frequency of an ion contributing to the overall signal (i.e. the target ion and two other non-target ions). The above equation may be expressed as:

[00018]${\mathrm{OP}}_1={?}_{11}{\mathrm{TP}}_1+{?}_{12}{\mathrm{TP}}_2+{?}_{13}{\mathrm{TP}}_3{\mathrm{OP}}_2={?}_{21}{\mathrm{TP}}_1+{?}_{22}{\mathrm{TP}}_2+{?}_{23}{\mathrm{TP}}_3{\mathrm{OP}}_3={?}_{31}{\mathrm{TP}}_1+{?}_{32}{\mathrm{TP}}_2+{?}_{33}{\mathrm{TP}}_3\mathrm{Here},{?}_{\mathrm{nm}}=e^{\frac{i\left({?}_{\mathrm{mk}}-{?}_n\right)T_E}{2}}*\frac{\sin \frac{\left({?}_m-{?}_n\right)T_E}{2}}{{?}_m-{?}_n}$ [0151] Where m refers to an ion oscillation at frequency ?.sub.m associated with an adjacent peak TP.sub.m, n refers to the frequency ?.sub.n of the component we are interested in.

[0152] Solving this set of simultaneous equation for: TP.sub.1, TP.sub.2, TP.sub.3, provides a corrected value (e.g. TP.sub.1, for the target ion) for any given one of the values of the frequency-domain signal to be used in the step of calculating the charge of the target ion, as described above.

[0153] In other words, rather than simply using the observed spectral peak value OP.sub.1 from the respective harmonic peak (H1 of FIG. 6) of the signal, the method may include using the true spectral peak value TP.sub.1 instead (i.e. OP.sub.1.fwdarw.TP.sub.1). The same procedure may be applied to each one of the values of the frequency-domain signal associated with the target ion (e.g. FIG. 6: the spectral peaks H1, H2 and H3) to obtain: [0154] (1) A true spectral peak value TP.sub.1.sup.(1) for the peak value of the harmonic spectral peak H1; [0155] (2) A true spectral peak value TP.sub.1.sup.(2) for the peak value of the harmonic spectral peak H2; [0156] (3) A true spectral peak value TP.sub.1.sup.(3) for the peak value of the harmonic spectral peak H3;

[0157] These three true spectral peak values (TP.sub.1.sup.(1), TP.sub.1.sup.(2), TP.sub.1.sup.(2) be used in the step of calculating the target ion charge.

[0158] The values of the frequency-domain signal to be used in the step of calculating the target ion charge are values of the amplitude or magnitude of the complex numbers representing the frequency-domain signal. In general, both, OP and TP are complex numbers taken at certain points on frequency spectrum. A Fourier Transform of a signal gives a complex number for each frequency point. When constructing the matrix of linear equations, described herein, one uses these complex numbers. This enables linearity of the system of equations. After the solutions TP are found (complex numbers) one may calculate the magnitudes of these complex numbers determined by calculating: Magnitude=sqrt({Re[TP]}.sup.2+{Im[TP]}.sup.2)) This calculation may be done for several points for each harmonic of each peak. With the determined magnitude of the target peak to hand, the charge of the associated ion may be calculated.

[0159] By taking these phase differences into account, the corrected M separate values (TP.sub.n) of the frequency-domain signal may be more accurate.

[0160] With reference to FIG. 9, which shows part of a frequency spectrum of two ions one of whichthe ion associated with peak #2changed its oscillation frequency at some point during the capture of the recorded signal. One can see that there are three spectral peaks located at three differing frequencies in the illustrated spectrum. Peak #1 is the target frequency of the target ion, and peaks #2 and #3 are interferences.

[0161] If peak #1 had been the only spectral peak within the section of the spectrum shown in FIG. 9, then its power spectrum would be represented by a single sinc-function and the task of establishing the magnitude of the spectral peak #1 for that frequency component would be straightforward. However, as can be seen from FIG. 9, when there are several frequency components (i.e. peaks #2 and #3), their individual spectra combine and, as a result, establishing the true magnitude of the target peak #1 is more complicated. Specifically, the observed spectral magnitude of peak #1, OP.sub.1, is a combination of its true magnitude, TP.sub.1, and the contributions from peaks #2 and #3 that are proportional to their respective true magnitudes.

[0162] If the phases of all three ions are the same, the above system of equations is linear with respect to the unknowns TP.sub.1, TP.sub.2 and TP.sub.3. This is because the phase of a frequency component m is factored in its coefficients ?.sub.nm and if this is the same for all components then these additional factors may be reduced to a common factor. In that case, all ?.sub.nm depend only on the difference between frequency positions of the components n and m within the spectrum, as there is no variation in the value of the common phase factor within the above system of equations. If this assumption is true, for example, when all ions would be considered to start at the same time and their initial phase would be the same. However, this assumption is not the case in most of the real experimental scenarios. If we assume that the phases of all components are not the same, then the above system of equations should include the phase factors with different phases for each of the components. These phase factors are treated as additional unknows and the system of equations becomes non-linear.

[0163] The signal processing unit 91 comprises a processor or computer programmed to execute computer program instructions to perform the above signal processing steps upon image charge/current signals representative of trapped ions undergoing oscillatory motion. The result is a value representative of the charge on the ion. The ion analyser 80 further incudes a memory unit and/or display unit 93 configured to receive data 92 corresponding to the charge on the ion, and to display the determined charge value to a user and/or store that value in a memory unit.

[0164] FIG. 2b shows a schematic drawing of the recorded image-charge/current signal generated by the ion analyser apparatus of FIG. 2a. The signal consists of an acquired signal transient that may typically be observed to exist for about a second, or less, and occurs when an ion undergoes oscillatory motion within an ion analyser apparatus (e.g. an ion trap) and in so doing induces an image-charge/current signal detectable by sensor electrodes of the apparatus configured for this purpose. The recorded image-charge/current signal comprises a plurality of pulses within the image-charge/current signal forming a periodic succession of repetitive signal pulses, with repetition period T. This one-dimensional time-domain image-charge/current signal is generated by an ion analyser 80 of FIG. 2a. The signal corresponds to the recorded image-charge/current signal 90 received by the signal processor 91 from the signal recording unit 89, and is representative of the oscillatory motion of one or more ions in the ion analyser apparatus. The signal consists of a sequence of regularly-spaced sequence of brief but intense, image-charge/current signal pulses (7 including: 7a, 7b, 7c, 7d, 7e, 7f, 7g, . . . and 8, etc.) each being separated, one from another, by intermediate intervals of mere noise in which no discernible transient signal pulse is present. Each signal pulse corresponds to the brief duration of time when an ion 85B, or a group of ions, momentarily passes between the two opposing image-charge/current sensing electrodes 87 of the electrostatic ion trap 80 during the oscillatory motion of the ion(s) within the ion trap.

[0165] The period of oscillations by definition is the time distance between two reflections e.g. states where ion kinetic energy is minimal and its potential energy is maximal. In symmetric systems, one can consider that an ion's oscillation period is the signal period.

[0166] A first pulse (7a) is generated when the ion(s) 85B passes the sensing electrodes 87, moving from left-to-right, during the first half of one cycle of oscillatory motion within the electrostatic trap, and a second pulse (7b) is generated when the ion(s) passes the sensing electrodes 87 again, this time moving from right to left during the second half of the oscillatory cycle. A subsequent, second cycle of oscillatory motion generates subsequent signal pulses (7c, 7d). The first half of the third cycle of oscillatory motion generates subsequent signal pulse (7e), and additional pulses follow as the oscillatory motion continues, one cycle after another.

[0167] Successive signal pulses are each separated, each one from its nearest neighbours, in the time-domain (i.e. along the time axis (t) of the signal), by a common period of time, T, corresponding to a period of what is, in effect, one periodic signal that endures for as long as the ion oscillatory motion endures within the electrostatic ion trap. In this way, the periodicity of the periodic signal is related to the period of the periodic, cyclic motion of the ion(s) within the electrostatic ion trap 80, described above. Thus, the existence of this common period of time (T) identifies the sequence of pulses (7, 8) as being a periodic component of the image-charge/current signal. Given that the common period of time, T, necessarily corresponds to a frequency (i.e. the inverse of the common time period), then this periodic component can also be described as a frequency component. The signal may be harmonic or may be non-harmonic, depending on the nature of the periodic oscillatory motion of the ion(s). Such a signal may be harmonic in the sense of having a waveform in the form of a sinusoidal wave. Otherwise it is non-harmonic which means it has one or more significant frequency components in addition to its fundamental harmonic component (e.g. e.g. other higher order harmonic frequency components, or non-harmonic frequency components).

[0168] The following method is an example of one possible way of determining the period, T, and the lifetime, T.sub.LT, of the periodic component within the recorded image charge signal. However, other methods for determining the lifetime of the ion oscillatory motion may be used, such as would be readily apparent to the skilled person, e.g. Short-Time Fourier Transform (STFT) methods, and the STORI method discussed above.

[0169] FIG. 2c shows a schematic representation of a 2D function, F.sub.2(t.sub.1,t.sub.2), comprising a stack of segmented portions of the image-charge/current signal, F.sub.1(t), schematically shown in FIG. 2b. This is an example of the 2D function defined by the data 92 generated by the signal processor 91 and output to the display unit 93. The signal processor 91 is configured to determine a value (T) for the period of the periodic component (7a, 7b, 7c, 7d, 7e . . . etc.) within the image-charge/current signal, F.sub.1(t), and then to segment the image-charge/current signal, F.sub.1(t), into a number of separate successive time segments of duration corresponding to the determined period. The signal processor is configured to subsequently co-register the separate time segments in a first time dimension, t.sub.1, defining the determined period (T). Next, the signal processor 91 separates the co-registered time segments along a second time dimension, t.sub.2, transverse (e.g. orthogonal) to the first time dimension. The result is to generate a stack of separate, successive time segments arrayed along the second time dimension. Collectively, this array of co-registered time segments defines the 2D function, F.sub.2(t.sub.1,t.sub.2), which varies both across the width of the stack in the first time dimension, t.sub.1, according to time within the determined period, T, and also along the length of the stack in the second time dimension, t.sub.2, according to time between successive time segments. Referring to FIG. 2c, the period, T, of the periodic component has been determined to be T=4.5 ?sec, and the continuous 1D image-charge/current signal has been segmented into a plurality of time segments (7A, 7B, 7C, 7D, 7E . . . etc.) each being 4.5 ?sec in duration. Each one of the time segments of the plurality of time segments has been co-registered with each one of the other time segments of the plurality of time segments. This means that the first time segment 7A is selected to serve as a reference time segment against which all other time segments are co-registered. To achieve this co-registration, the time coordinate (i.e. the first time dimension t.sub.1) of each signal data value/point in a given time segment, other than the reference time segment1 is subject to the following transformation of 1D time (t) into 2D time (t.sub.1, t.sub.2), in order to implement a step of segmenting the recorded signal into a number of separate time segments. The result is to convert the 1D function, F.sub.1(t), into the 2D function, F.sub.2(t.sub.1, t.sub.2), according to the relation:

[00019]$t.fwdarw.t_1+t_2{F}_1\left(t\right).fwdarw.F_2\left(t_1,t_2\right)?F_1\left(t_1+t_2\right).$

[0170] Here the variable t.sub.1 is a continuous variable with values restricted to be within the time segment, [0;T], ranging from 0 to T, where T is the period of the periodic component. The variable t.sub.2 is a discreet variable with values constrained such that t.sub.2=mT, where m is an integer (m=1, 2, 3 . . . , M). The upper value of m may be defined as: M=T.sub.acq/T, where T.sub.acq is the acquisition time, which is the total time duration over which all of the data points are acquired.

[0171] In other words, segmentation may be performed by enforcing these restrictions, such that each separate value of the integer m defines a new segment and a step along the second time dimension, t.sub.2. Each segment has a time-duration, in the first time dimension t.sub.1, ranging from t.sub.1=0 to t.sub.1, =T only. This also means that the beginning time point of each segment shares the same value of the continuous time variable t.sub.1 (i.e. t.sub.1=0) with the beginning time point of every other segment, but has a unique value of time t.sub.2 in the second time dimension Similarly, this also means that the end time point of each segment shares the same value of the continuous time variable t.sub.1 (i.e. t.sub.1=T) with the end time point of every other segment, but has a unique value of t.sub.2 in the second time dimension. In this sense, the different segments are co-registered (i.e. aligned in time) with each other in the 2D space of the 2D function, F.sub.2(t.sub.1, t.sub.2). Of course, it is to be understood that the actual sampled value of the image-charge/current signal are discrete values which are sampled at a finite number of discrete time points within the continuous time interval, [0;T]. This means that actual measured signal values may or may not exist (depending on the sampling rate etc.) at the exact point in time: t.sub.1=0, t.sub.1=T, in the segments.

[0172] For example, the step of segmenting the recorded signal into a number of separate time segments may include converting the 1D function, F.sub.1(t), into the 2D function, F.sub.2(t.sub.1, t.sub.2), according to the relation:

[00020]$F_{\mathrm{nm}}?F_1\left(\frac{n}{N}T+\mathrm{mT}\right)\mathrm{Here},\frac{n}{N}T=t_1,\mathrm{mT}=t_2$

[0173] In addition, the integer N denotes the number of data points (measurements or samples) that are available within the segment time interval [0;T]. For example, the data sampling time interval, ?t, may be such that ?t=T/N, and the counting integer n varies in the range n=1, 2, . . . , N. In other words, the step of segmenting may produce a matrix, F.sub.nm, of data values comprising m rows and n columns. Each row of the matrix defines a unique segment, with successive rows defining a stack of segments. The row dimension of the row of the matrix corresponds to the first time dimension, t.sub.1, whereas the column dimension of the matric corresponds to the second time dimension, t.sub.2. In this sense, the different segments are co-registered (i.e. aligned in time) with each other, and separated from each other, in the 2D space of the 2D function, F.sub.2(t.sub.1, t.sub.2).

[0174] The result is equivalent to a common time displacement or translation (schematically represented by item 25 of FIG. 2c) in a negative time direction along the first time dimension sufficient to ensure that the translated time segment starts (21, 23, . . . etc.) at time t.sub.1=0 and ends (22, 24, . . . etc.) at time t.sub.1=T=4.5 psec. The result is that each time segment (7A, 7B, 7C, 7D, 7E . . . etc.) receives its own appropriate time translation (see item 25 of FIG. 2c) sufficient to ensure that all time segments extend only within the time interval [0;T] along the first time dimension.

[0175] It is important to note that this registration process applies to time segments as a whole and does not apply to the location of transient signal pulses (7a, 7b, 7c, 7d, 7e, . . . etc.) appearing within successive time segments. However, if the time period, T, for the periodic signal component has been accurately determined, then the result of co-registering the time segments will be the consequential co-registration of the transient signal pulses, and the position of successive transient pulses along the first time dimension, will be static from one co-registered time segment to the next. This is the case in the schematic drawing of FIG. 2c, in which we see that the transient signal pulses align along a linear path parallel to the axis of the second time dimension.

[0176] Conversely, if the time period, T, for the periodic signal component has not been accurately determined, then the result of co-registering the time segments will not result in a co-registration of the transient signal pulses, and the position of successive transient pulses along the first time dimension, will change/drift from one co-registered time segment to the next.

[0177] The signal processor 91 subsequently displaces, or translates, each one of the co-registered time segments along a second time dimension, t.sub.2, which is transverse (e.g. orthogonal) to the first time dimension. In particular, each signal data value/point in a given time segment, other than the reference time segment1 is assigned an additional coordinate data value such that each signal data point comprises three numbers: a value for the signal; a time value in the first time dimension and a value in the second time dimension. The first and second time dimension values, for a given signal data point, define a coordinate in a 2D time plane, and the signal value associated with that data point defines a value of the signal at that coordinate. In the example shown in FIG. 2c, the signal value is represented as a height of the data point above that 2D time plane.

[0178] The time displacement or translation applied along the second time dimension is sufficient to ensure that each translated time segment is spaced from its two immediately neighbouring co-registered time segments, i.e. those immediately preceding and succeeding it, by the same displacement/spacing. The result is to generate a stack of separate, successive time segments arrayed along the second time dimension, which collectively defines the 2D function, F.sub.2(t.sub.1,t.sub.2), as shown in FIG. 2c. This function varies both across the width of the stack in the first time dimension, t.sub.1, so as to indicate the position and shape of the transient signal pulse within the time [0;T], and also along the length of the stack in the second time dimension, t.sub.2, according to time between successive time periods, or stack-segment number. Since the time interval between the beginning of the n.sup.th and (n+1).sup.th stack, or between any two points with the same coordinate in the first time dimension, is necessarily equal to the time period, T, then the successive time segments are inherently spaced along the second time dimension by a time interval of T seconds (e.g. 4.5 ?sec in the example of FIG. 2c).

[0179] FIG. 2d schematically represents the procedure for determining a value, T, for the period of the periodic signal component within the image-charge/current signal, F.sub.1(t), in the method for generating the 2D function F(t.sub.1,t.sub.2). The first step in the method is to generate an image charge/current signal, and then to record the image charge/current signal in the time domain.

[0180] The acquired recording of the one-dimensional time domain image-charge/current signal, F.sub.1(t) of FIG. 2d, contains one or more periodic oscillations. These periodic components may correspond to frequency components f.sub.1=1/T.sub.1, f.sub.2=1/T.sub.2 . . . etc.

[0181] Subsequently, the next step of the method determines a period (T) for a periodic signal component within the recorded signal, and this step may comprise the following sub-steps: [0182] (1) A first sub-step is to sample the one-dimensional time domain signal F.sub.1(t) of FIG. 2d, with a sampling step of size ?t. [0183] (2) A second sub-step is to estimate a value for the time period, T.sub.i(i=1, 2, . . . ), of each of the periodic/frequency components f.sub.1=1/T.sub.1, f.sub.2=1/T.sub.2 . . . etc. This may be done by means of any suitable spectral decomposition method as would be readily apparent to the skilled person, or may be done purely by initially guessing those values and applying the present methods iteratively until a consistent result is found. [0184] (3) A third sub-step is to segment the one-dimensional signal, F.sub.1(t), and co-register the time segments according to a chosen period (frequency) value, f.sub.i=1/T.sub.i, so as to form the 2D function F(t.sub.1,t.sub.2). In particular, the argument t.sub.1 starts at t.sub.1=0 (zero) and every subsequent sampling step increases along the t.sub.1 axis by a step-size ?t: initially the argument t.sub.2=0 (zero) during this process. After time t.sub.1 is equal to or greater than T has been reached, the argument t.sub.1 is reset to t.sub.1=0 (zero) and the argument t.sub.2 increases by a step size of T, i.e. t.sub.2=T. Thus, each sampling point of the measured signal is attributed to a pair of values, (t.sub.1, t.sub.2). In this way a 2D mesh/plane (t.sub.1, t.sub.2) is formed. This constitutes a separating of the co-registered time segments along a second time dimension, t.sub.2, transverse to the first time dimension thereby to generate a stack of time segments collectively defining a 2-dimensional (2D) function. The resulting function F.sub.2(t.sub.1,t.sub.2) can be thought of as a set of layers F(t.sub.1) where t.sub.1 is always within interval [0;T] and each layer corresponds to a certain t.sub.2 having a constant value (an integer multiple of T) within the layer. [0185] (4) A fourth sub-step, according to a first option, is to generate a first 2D scatter graph such that F(t.sub.1, t.sub.2=fixed), ignoring variation in t.sub.2 values, corresponds to viewing F.sub.2(t.sub.1,t.sub.2) along View (a) of FIG. 2c, and will result in all layers been seen to overlap onto each other. For a proper choice of segment period, T, a peak can be seen above noise area, as shown in FIG. 2e. [0186] (5) A fourth sub-step, according to a second option, is to generate a second 2D scatter graph which corresponds to viewing F.sub.2(t.sub.1,t.sub.2) along View (b) of FIG. 2c, showing F.sub.2(t.sub.1,t.sub.2) subject to the following condition: plot point (t.sub.2;t.sub.1) if |F.sub.2(t.sub.1,t.sub.2)|<C where C is predetermined threshold value (e.g. a pre-defined signal level), otherwise skip/omit it from the plot. For a proper choice of segment period, T, a clear channel of width ?t.sub.1 in FIG. 2f, substantially free of data points, will appear to extend along a path parallel to the t.sub.2 axis, surrounded/bounded by points as shown in FIG. 2f. It is to be understood that the condition |F.sub.2(t.sub.1,t.sub.2)|>C is also possible, and this condition this will make a filled channel with clear space around it in the 2D space.

[0187] The value for the period, T, may be arrived at iteratively, using procedures (4) or/and (5) to decide whether the chosen period value corresponding to a frequency component of signal F.sub.1(t). This decision may be based on certain criteria. For example, according to method step (4), if the representation of F.sub.2(t.sub.1,t.sub.2) contains a peak-shaped dense area then this is categorized as a frequency component. Examples are shown in FIG. 2e. Alternatively, or in addition, according to method step (5), for a pre-defined signal threshold level, C, if the representation of F.sub.2(t.sub.1,t.sub.2) contains a clear and substantially straight channel (item 6 of FIG. 2f) extending along a path parallel to t.sub.2 axis, then this is categorized as a frequency component. An example is shown in FIG. 2f. Both methods provide a means of identifying when the chosen segment period, T, (i.e. the length of each time segment) accurately matches the actual time period of the periodic component within the signal, F.sub.1(t). Only then will each transient peak of the periodic component in successive time segments line-up in a linear fashion along a path parallel to the axis of the stacking dimension (t.sub.2). If the chosen segment period, T, does not accurately match the actual time period of the periodic component within the signal, F.sub.1(t), then the transient peak of the periodic component in successive time segments will not line-up in a linear fashion along a path parallel to the axis of the stacking dimension. Instead, the peaks will drift along a path diverging either towards the axis of the stacking dimension, or away from it.

[0188] Non-iterative methods of determining the frequency are also possible. Such methods may be faster. For example, suppose that the period of the periodic component that is initially determined, is slightly incorrect (i.e. T?T, but not by much). The result is a linear feature extending through the 2D space of the 2D function in a direction inclined to the second time dimension (t.sub.2 axis). One may find the period corresponded to this signal iteratively as described above, by iteratively re-segmenting and re-stacking the original 1D signal again and again until the linear feature is made parallel to the t.sub.2 axis. Alternatively, one can determine an inclination angle which the linear path of the linear feature subtends to the axis of the first time dimension (e.g. with respect to t.sub.1 axis) and get correct stacking period (i.e. T=T), according to that angle (i.e. the angle between the t.sub.1 axis and linear path direction). The advantage is one does not need to perform iterative re-segmenting and re-stacking at all. This saves lots of computational time because usually a signal array in memory is a very large amount of data and accessing such arrays in a PC memory is a long process and is a bottleneck in processing speed. Once one has determined the inclination angle, the formula for the correct period, determined using the incorrect stacking period (T) and the inclination angle, is:

[00021]$\frac{1}{T}=\frac{1}{T^{}}\left(1+\frac{1}{\tan \left(?\right)}\right)$

[0189] The inclination angle, ?, can be measured directly, and may be iteratively optimized by successive measurements of the inclination angle, ?, made by successive versions of the linear feature for successive (improving) values of stacking period (T). In this way, the inclination angle, ?, can be used as an optimisation variable to find the condition T=T. Optimization methods readily available to the skilled person (e.g. gradient descent) or by machine learning tools (e.g. neural networks) may be used to implement this.

[0190] Either method, namely method (4) or method (5), may be performed either by image analysis algorithms or by numerical algorithms. Preferably, such algorithms would consider the density, or number, of data points on the respective representation of F.sub.2(t.sub.1,t.sub.2). For example, an algorithm may determine the number of points falling below a pre-defined threshold |F.sub.2(t.sub.1,t.sub.2)|<C within a pre-defined time interval ?t.sub.1 within the first time dimension. If the density, or number, of points is less than the threshold, C, then this may be used to indicate that the frequency component is suitably detected. FIG. 2f exemplifies this method. Here the method includes determining a sub-set of instances of the 2D function in which the value of the 2D function falls below the pre-set threshold value, C. From amongst that sub-set of instances one determines the interval of time, ?t.sub.1, in the first time dimension during which the 2D function never falls below the pre-set threshold value. One may then identify that interval of time as being the location/presence of the priodic signal component.

[0191] Algorithms may employ machine learning techniques including neural networks trained to classify images having resolved peak structures (method (4)) and/or noticeable channels (method (5)).

[0192] Once a value for the period, T, has been arrived at iteratively, the method proceeds by segmenting the recorded signal into a number of separate successive time segments of duration corresponding to the determined period. The procedure for doing this is the same as that described in the sub-step (3). It will be appreciated that, according to the iterative method of determining the time period, T, one inherently performs method sub-step (3) when one implements the final, successful sub-step (4) or (5) described above.

[0193] The final step of the method is to generating a stack of the time segments of the previous step, in a second time domain, t.sub.2, to generate a stacked image charge/current signal. The procedure for doing this is the same as that described in the sub-step (3) for co-registering the separate time segments in a first time dimension, t.sub.1, defining the determined period, T, and of separating the co-registered time segments along the second time dimension, t.sub.2, transverse to the first time dimension. Once more, according to the iterative method of determining the time period, T, one inherently performs the final step when one implements the final, successful sub-step (4) or (5) of step S3, described above.

[0194] In this method the signal processing unit may be programmed to determine the value, T, for the period of a periodic signal component iteratively in this way. It may initially estimate a trial value of T, as described above, and segment the recorded signal, F.sub.1(t), using that trial value, into a number of time segments of duration corresponding to a trial period, and co-registering them, then separate the co-registered time segments along the second time dimension, t.sub.2, to generate a stack of time segments. The signal processor unit may be configured to automatically determine whether the position of the periodic component (transient peak) in the first time dimension changes along the second time dimension. If a change is detected, then a new trial time period, T, is chosen by the signal processor and a new stack of time segments is generated using the new trial time period. The signal processor then re-evaluates whether the position of the periodic component (transient peak) in the first time dimension changes along the second time dimension, and the iterative process ends when it is determined that substantially no such change occurs. This condition signifies that the latest trial time period, T, is an accurate estimate of the true time period value.

[0195] With the value (T) of the period of the oscillatory motion of the target ion to hand, one may then proceed by truncating the recorded signal, F.sub.1(t), as follows.

[0196] Referring to FIGS. 3, 4 and 5, there is illustrated a procedure for truncating the recorded signal to provide a truncated signal having a duration substantially equal to an integer multiple (N?T) of period (T) of the period of the oscillatory motion of the target ion.

[0197] In particular, FIG. 3 shows a schematic view of a Fourier spectrum, in the frequency-domain, resulting from applying a Fourier transform to the recorded signal, F.sub.1(t). The Fourier spectrum possesses multiple clear spectral peaks (H1, H2, H3) rises clearly above a background spectral signal level 60. The first spectral peak, H1, is located at a lower frequency than the location of the second and third spectral peaks (H2, H3). This peak corresponds to the frequency of a first (fundamental) harmonic of the oscillatory motion of the target ion and encompasses a narrow range of frequencies including the fundamental frequency (f.sub.0=1/T, Hz) of the oscillatory motion of the target ion.

[0198] A second spectral peak, H2, is located at a mid-frequency between the location of the first and third spectral peaks (H1, H3). This peak corresponds to the frequency (2f.sub.0=2/T Hz) of a second harmonic (first overtone) of the oscillatory motion of the target ion and encompasses a narrow range of frequencies including the fundamental frequency of the oscillatory motion of the target ion.

[0199] A third spectral peak, H3, is located at a higher frequency beyond the location of the first and second spectral peaks (H1, H2). This peak corresponds to the frequency (3f.sub.0=3/T Hz) of a third harmonic (second overtone) of the oscillatory motion of the target ion and encompasses a narrow range of frequencies including the fundamental frequency of the oscillatory motion of the target ion. Other spectral peaks exist (not shown) at ever higher harmonic frequencies within the Fourier spectrum. Higher harmonics are responsible for the peak shape in the time domain within the recorded signal, F.sub.1(t). The decay of the recorded signal in the time domain is characterised by the peak shape in the frequency domain. For example, the shape of the decay of the signal peaks 8 within the recorded signal shown in FIG. 5. This decay in signal peaks begins when the regular oscillatory motion of the target ion begins to die and the oscillatory motion becomes more complex and contaminated with significant spectral (frequency) components that are not pure harmonics such as H1, H2 and H3 etc. The lifetime of the regular oscillatory motion of the ion has at that point in time effectively expired.

[0200] The procedure for truncating the recorded signal, to provide a truncated signal, aims to remove from the recorded signal those parts that are not within the lifetime of the target ion, thereby to clean the recorded signal before subsequent analysis of it.

[0201] It is necessary to determine an accurate estimate for the point in time (T.sub.Life) as measured from the beginning of the recorded signal, F.sub.1(t), at which the lifetime of the regular oscillatory motion of the ion has expired, and thereby estimate which parts of the recorded signal to remove by truncation. To perform this estimate, one may select as the truncated signal the sub-portion of the recorded signal which starts at a recorded time coinciding with (or after) the recorded start time of the recorded image-charge/current signal and ends at a recorded time before the recorded end time of the recorded image-charge/current signal.

[0202] The truncated signal may be a sub-portion of the recorded signal within which a sequence of repeating signal peaks reside which each have a respective peak signal value which deviates by not more than about 20% from the value of the largest peak value amongst the sequence of repeating signal peaks.

[0203] Alternatively, the truncating of the recorded signal may comprise the following steps illustrated with reference to FIG. 3 and FIG. 4: [0204] (1) First, the recorded signal, F.sub.1(t), is transformed into a frequency-domain, such as by applying a Fourier transform to it. This results in a spectrum such as shown in FIG. 3, thereby to generate a transformed recorded signal. [0205] (2) Selecting a harmonic spectral peak (e.g. H3) from within the spectrum. From within the selected harmonic peak: [0206] a. Select a peak value (?.sub.Peak, e.g. the maximum value 62) of the transformed recorded signal within the selected harmonic peak; then, [0207] b. Select a first adjacent value 61 (?.sub.FA) of the transformed recorded signal within the selected harmonic peak and corresponding to a frequency less than the frequency associated with the peak value by an amount ??.sub.FA; then, [0208] c. Select a first adjacent value 63 (?.sub.SA) of the transformed recorded signal within the selected harmonic peak and corresponding to a frequency greater than the frequency associated with the peak value by an amount ??.sub.SA. (e.g. |??.sub.FA|=|A?.sub.SA|). [0209] (3) Reconstruct a time-domain signal (51, 53, 54) as shown in FIG. 4, based on the selected peak value 62, the selected first adjacent value 61 and the selected second adjacent value 63. Reconstruction produces an approximate version, F.sub.1Approx(t), of the recorded signal F.sub.1(t) based purely on a few selected samples from within a spectral harmonic peak within the frequency spectrum of the recorded signal. [0210] (4) Determine a threshold time (T.sub.Like) at which an amplitude modulation 50 within the reconstructed time-domain signal falls below a threshold signal value. This threshold value may be set at about 80% of the maximum value of the first signal pulse 51, or of the maximum value of the amplitude modulation envelope 50. For example, in the schematic of FIG. 4, the first signal pulse 51 has an amplitude substantially matching the amplitude modulation envelope 50, and the fourth signal pulse 53 has an amplitude which is less than that of the first pulse, it being modulated by the amplitude modulation envelope 50, but still exceeds the threshold level. However, the fifth signal pulse 54 has an amplitude which is less than the threshold, it being further modulated by the amplitude modulation envelope 50. As a consequence, the threshold time (T.sub.Life) falls at a time between the times of pulses 53 and 54. [0211] (5) Truncate the recorded signal according to the threshold time (T.sub.Life) so determined.

[0212] It has been found that this method of reconstructing a version of the time-domain signal using only a few (e.g. three) frequency samples selected at and around the top of a spectral harmonic peak, is effective at capturing sufficient spectral information necessary to determine an accurate estimate for the time point at which the lifetime of the regular oscillatory motion of the ion has expired, and thereby estimate which parts of the recorded signal to remove by truncation. This method captures spectral information more specifically associated with the dynamics of the target ion and less contaminated by information regarding noise or regarding the dynamics of other interfering ions present in the recorded signal, F.sub.1(t). A suitable spectral peak has been found to be one which is a higher harmonic (the further from the fundamental harmonic the better) which is strong in the sense of being a sufficiently large peak not excessively influenced by noise (e.g. a sufficiently high signal-to-noise ratio).

[0213] With the value of the lifetime of the ion oscillatory motion to hand, together with a value of the period, T, of the oscillatory motion of the ion, one may proceed to truncate the recorded signal, F.sub.1(t) by defining a truncated lifetime (T.sub.trunc) of the ion which satisfies the following two conditions: [0214] (1) The truncated lifetime is substantially equal to an integer (N) multiple of the period (T) of the oscillatory motion of the target ion: i.e. T.sub.trunc=N?T. [0215] (2) The truncated lifetime is less than the lifetime (T.sub.Life) of the regular oscillatory motion of the ion.

[0216] FIG. 5 shows this relationship schematically.

[0217] Processing of a cleaner version of the time-domain signal may then proceed based on frequency-domain harmonic components (e.g. H1, H2, H3 . . . etc., in FIG. 5) from within this truncated time-domain signal. That is to say, the method proceeds by applying a transform of the truncated signal, such as a Fourier transform, to provide a frequency-domain spectrum of the truncated time-domain signal. From this spectrum, a selection is made of one or more values of the spectral signal corresponding to a respective one or more harmonic peaks within the spectrum.

[0218] On the basis of these one or more values of the spectral signal the cleaner version of the frequency-domain signal is used for calculating the charge of the target ion. FIGS. 5 and 6 illustrate aspects of this process schematically.

[0219] This method provides a means for estimating ion charge values based on cleaning of the image-charge/current signal's frequency spectrum, followed by reconstitution of the signal from this cleaned frequency spectrum. Whereas, in the prior art, cleaning of a frequency spectrum is usually done by removing or modifying all of the frequency components of the spectrum that are deemed to be noise or non-essential, the present invention implements a different strategy. For example, in CDMS, once an ion oscillation is identified in a Fourier spectrum, we are interested in the magnitudes of spectral peaks, which means that the useful components of a spectrum are frequency ranges around peak tops. Noise frequencies that fall within those frequency ranges cannot be removed during prior art spectrum cleaning methods.

[0220] However, in the present method illustrated by FIG. 5, one reduces (truncates) the size of the input time-domain image-charge/current signal data set, so that it covers e.g. slightly less than the lifetime of ion oscillation and so that the duration of the truncated data set substantially equals to an integer number of period (T=1/F) of the fundamental harmonic of oscillatory motion of the target ion. This makes the time-domain signal approximately satisfy the ideal periodical boundary condition, and, after application of a frequency transform (e.g. Fourier transform) to the truncated time-domain signal, the target frequency spectral peaks (harmonic peaks) in the frequency domain spectrum become much narrower (e.g. an equivalent of the delta function), in the present method illustrated by FIG. 6. This makes the task of selecting a spectral peak value, from within a spectral peak, much more accuratei.e. selecting the peak value of a very narrow peak shape, as opposed to a broader peak shape. The act of truncating the recorded image-charge signal to be not greater than the lifetime of the oscillatory motion of the ion is responsible for the majority of the narrowing of the spectral peaks. The act of additionally truncating the recorded image-charge signal so that its duration is also equal to an integer number of periods, T, is responsible for reducing scalloping loss in the frequency-domain signal.

Effects of Signal Truncation on Fourier Spectral Values

[0221] Without wishing to be bound by theory, the following discussion aims to provide a better understanding of the invention by reference to illustrative theoretical principles and notional examples. To aid a better understanding of the invention, the following discussion explores the effects of truncation of a notional, idealised image-charge current signal of total duration TR which includes within it a pure sinusoidal wave with the period T.sub.0 and lifetime duration LT?TR (see FIG. 11). This discussion is particularly interested in illustrating the effects of truncation of this signal on its Fourier spectrum.

[0222] The following aims to show how the truncation of the length of the signal, TR, to an integer multiple of the periods T.sub.0 affects the signal's Fourier spectrum. Of particular interest are the following two cases:

[00022]$\begin{array}{cc}\mathrm{When}\mathrm{LT}=\mathrm{TR}& \left(1\right)\end{array}$$\begin{array}{cc}\mathrm{When}\mathrm{LT}<\mathrm{TR}.& \left(2\right)\end{array}$

[0223] A general formula which is derived below (see Theoretical Background) for the spectral value A(?) of the Fourier spectrum of the signal A.sub.?0 cos(?.sub.0t+?), at a frequency point ?, is:

[00023]$A\left(?\right)=A_{{?}_0}*e^{i?}*e^{\frac{i\left({?}_0-?\right)\left(T_S+T_E\right)}{2}}*\frac{\sin \frac{\left({?}_0-?\right)\left(T_E-T_S\right)}{2}}{{?}_0-?}$

[0224] Here, ?.sub.0 is the frequency of the sinusoidal wave (we do not differentiate between the sine and cosine since that is merely a matter of choosing the phase); ? is the initial phase of the sine wave; A.sub.?0 is its amplitude; T.sub.S and T.sub.E are, respectively, the start and end times of the sine wave.

[0225] For simplicity, we set A.sub.?0=1, ?=0, T.sub.S=0, T.sub.E=LT. With this, the above formula transforms into the following expression:

[00024]$A\left(?\right)=e^{\frac{i\left({?}_0-?\right)\mathrm{LT}}{2}}*\frac{\sin \frac{\left({?}_0-?\right)\mathrm{LT}}{2}}{{?}_0-?}=\frac{\mathrm{LT}}{2}*e^{\mathrm{iy}}*\mathrm{sinc}\left(y\right)\mathrm{Here},y=\frac{\left({?}_0-?\right)\mathrm{LT}}{2}\mathrm{and}\mathrm{sinc}\left(x\right)=\frac{\sin \left(x\right)}{x}$

[0226] Of interest is the magnitude, M(?), of A(?), and the above can be reduced to:

[00025]$M\left(?\right)=.Math.A\left(?\right).Math.=\frac{\mathrm{LT}}{2}*\mathrm{sinc}\left(y\right)$

[0227] Note that if ?.fwdarw.?.sub.0, then y.fwdarw.0 and M(?).fwdarw.LT/2 and this value does not depend on TR. The discrete Fourier transform (DFT) of a signal of duration TR results in a sequence of spectral values equally spaced along the frequency axis with the distance between two adjacent points (frequency bins) given by:

[00026]$?f=\frac{1}{\mathrm{TR}}$

[0228] Thus, the values of ? where spectral values exist are given by:

[00027]${?}_m=\frac{2?m}{\mathrm{TR}}$

where 0?m?N and N is the total number of signal samples. Note that while the values of ?.sub.m are defined completely by the value of TR, ?.sub.0 is arbitrary and it may or may not coincide with one of the ?.sub.m. Thus, we can re-write the expression:

[00028]$y=\frac{\left({?}_0-?\right)\mathrm{LT}}{2}$

in terms of indexes m.sub.0 and m, as:

[00029]$y=\frac{?\left(m_0-m\right)\mathrm{LT}}{\mathrm{TR}}=?\left(m_0-m\right)?$

where ?=LT/TR, index m is always an integer number and index m.sub.0 is not necessarily an integer number. If we want m.sub.0 to be integer, then TR must satisfy the condition:

[00030]$\mathrm{TR}=\frac{2?m_0}{{?}_0}=T_0*m_0$

[0229] In other words, TR must be truncated to an integer number of periods T.sub.0. The final expression for M(?) becomes:

[00031]$M^{}\left(m\right)=\frac{LT}{2}*\frac{\sin \left[?\left(m_0-m\right)?\right]}{?\left(m_0-m\right)?}$

[0230] Note that, strictly speaking, M and M are different functions. Let us consider scenarios: [0231] (A) with m.sub.0 coinciding with one of the frequency bins which happens when TR is truncated to an integer number of T.sub.0's; and [0232] (B) with m.sub.0 half-way between two adjacent frequency bins. This is the worst case scenario with a non-truncated TR, as is schematically shown in FIG. 12.

[0233] Table 1 below shows the values of:

[00032]$\frac{2}{LT}{M}^{}\left(m\right)$

for scenarios A and B above for different values of ?=LT/TR:

TABLE-US-00002 TABLE 1 LT/TR m m-1 m-2 A. Truncated 1.00 1.000 0.000 0.000 B. Untruncated 0.637 0.212 0.127 A. Truncated 0.90 1.000 0.109 0.104 B. Untruncated 0.699 0.210 0.100 A. Truncated 0.50 1.000 0.637 0.000 B. Untruncated 0.900 0.300 0.180 A. Truncated 0.10 1.000 0.984 0.935 B. Untruncated 0.996 0.963 0.900

[0234] Table 1 shows that the extent of benefits from truncation of the signal depends on the LT/TR ratio. In particular, if the input signal contained no noise at all, then truncate the signal would provide no noise-reduction benefit. In that case one would be able to reconstruct the underlying sinc function using any two spectral values selected from the frequency axis.

[0235] However, the situation is quite different in the presence of noise. In this case it is important to get as high signal-to-noise (S/N) ratio in the input data, as possible. This is because the higher the S/N, the less distortion by noise we get in the unput data and, therefore, in the useful information we extract from those data. If we are interested in estimating spectral values at (or close to) the apexes of spectral peaks in the Fourier spectrum, then truncation will result in improvement of the S/N ratio (e.g. see the values for column m in the above table).

[0236] FIG. 7 shows the result of the reconstructed time-domain image-charge/current signal 11 after the cleaning, together with the original recorded image-charge/current signal 10 for comparison. The reconstructed signal 11 has unnecessary noise eliminated which makes it easy to measure the magnitude of the image charge signal accurately.

[0237] In cases where the target ion's oscillatory motion has a well-defined period, thereby having very well defined dominant harmonic frequency values in its frequency spectrum, the frequency spectrum of the truncated signal may comprise very sharp and spectral components allowing accurate determination of an appropriate peak spectral signal value at the top of a given spectral peak, in the present method illustrated by FIG. 6. In cases where the target ion's oscillatory motion is non-harmonic, such as the motion one expects from the ELIT or the Orbital frequency analyser, the widths of spectral peaks broadens and all spectral points apart from those at harmonic frequencies (i.e. integer multiples of the fundamental harmonic frequency, F.sub.0. e.g. F=nF.sub.0 for n=1, 2, 3, . . . ) represent noise and are non-essential signals to be removed by the above cleaning process. This maximises the reduction of noise-related spectral power from the image-charge/current signal's frequency spectrum. After such cleaning, far fewer data points remain in the frequency spectrum. The width (and shape) of an isolated spectral peak defines the envelope of the respective time domain signal. It is not (generally speaking) noise or non-essential signal.

Theoretical Background

[0238] Without wishing to be bound by theory, the following discussion aims to provide a better understanding of the invention, e.g. in relation to the use of the simultaneous equations defined above, by reference to illustrative theoretical principles and notional examples.

The Problem to Solve

[0239] Assume an image-charge current signal of a known length produced by oscillating ions of different charges. An ion may appear at an arbitrary moment of time, T.sub.S, and disappear at an arbitrary moment of time T.sub.E. By definition, lifetime of an ion is LT=T.sub.E?T.sub.S. This is illustrated in FIG. 13. The task is to determine the charges of the ions. Neither T.sub.S nor T.sub.E are known, nor is the number of ions. In addition, in many real experiments the level of noise may exceed the level of the useful signal by almost two orders of magnitude, so that no individual ions' contributions are discernible by eye in the time domain signal as shown in FIG. 14.

Fourier Transform

[0240] One can take the Fourier Transform (FT) of the time domain image-charge current signal and obtain its frequency spectrum. However, estimation of the charges may become less accurate if these ions undergo oscillatory motion at very similar frequencies leading to spectral interference. The heights of the peaks in the frequency spectrum depend not only on the ions' charges, but also on their lifetimes (LT). In addition, the widths of these peaks depend on ion lifetimes (LT), and adjacent peaks may interfere with each other as illustrated in FIG. 9. FIG. 9 shows part of a frequency spectrum of two ions one of whichthe ion associated with peak #2changed its oscillation frequency at some point during the capture of the recorded signal. One can see that there are three spectral peaks located at three differing frequencies in the illustrated spectrum. Peak #1 is the target frequency of the target ion, and peaks #2 and #3 are interferences.

[0241] If peak #1 had been the only spectral peak within the section of the spectrum shown in FIG. 9, then its power spectrum would be represented by a single sinc-function and the task of establishing the magnitude of the spectral peak #1 for that frequency component would be straightforward. However, as can be seen from FIG. 9, when there are several frequency components (i.e. peaks #2 and #3), their individual spectra combine and, as a result, establishing the true magnitude of the target peak #1 is more complicated. Specifically, the observed spectral magnitude of peak #1, OP.sub.1, is a combination of its true magnitude, TP.sub.1, and the contributions from peaks #2 and #3 that are proportional to their respective true magnitudes.

[0242] One can establish from the peaks within the spectrum of FIG. 9 the number of oscillating ions (three) and their frequencies. Each peak corresponds to a different ion and, using higher harmonics of the signal, the frequencies of these ions can be established with reasonable accuracy. Further analysis may be p[referable to improve the accuracy of an estimate of the charges of those ions. This is because the heights of the peaks depend on the charges, the LTs of the respective ion image-charge current signal, and any contributions/interferences from the adjacent peaks. For example, the three peaks in FIG. 9 were produced by ions with the same charge of 50e. For each peak, one can say that its observed peak height, OP, is a combination of its true peak height, TP, and contributions of the adjacent true peak heights. Each peak's contribution could be expressed as ?TP, where TP is the true (yet unknown) height of the peak and a is a coefficient that depends on the ion's LT and charge.

[0243] Thus, for N ions we have a system of equations:

[00033]$\begin{array}{cc}\begin{array}{c}{\mathrm{OP}}_1={?}_{11}{\mathrm{TP}}_1+{?}_{12}{\mathrm{TP}}_2+.Math.+{?}_{1N}{\mathrm{TP}}_N\\ {\mathrm{OP}}_2={?}_{21}{\mathrm{TP}}_1+{?}_{22}{\mathrm{TP}}_2+.Math.+{?}_{3N}{\mathrm{TP}}_N\\ .Math.\\ {\mathrm{OP}}_N={?}_{N1}{\mathrm{TP}}_1+{?}_{N2}{\mathrm{TP}}_2+.Math.+{?}_{NN}{\mathrm{TP}}_N\end{array}& \left[1\right]\end{array}$

[0244] The above system must be solved with respect to TPs. The following shows that the individual peaks' contributions are linear with respect to peaks' heights, TP, and that the coefficients ? may be non-linear with respect to T.sub.S and T.sub.E.

Useful Formulas

[0245] A useful expression for the Fourier Transform (FT) of the following function:

[00034]$f\left(t,{?}_0\right)=\{\begin{array}{c}{e}^{i{?}_{0}t},t?\left[T_S,T_E\right],\\ 0,t<T_S,t>T_E\end{array}$

is given by:

[00035]$\left(?\right)=\mathrm{FT}\left(f\left(t\right)\right)={?}_{-?}^{+?}{e}^{-i?t}*e^{i{?}_{0}t}\mathrm{dt}={?}_{T_S}^{T_E}{e}^{-\left(i?-i{?}_0\right)t}\mathrm{dt}=\frac{e^{i\left({?}_0-?\right)T_{E-e}i\left({?}_0-?\right)T_S}}{i\left({?}_0-?\right)}$

[0246] Introducing ?.sub.?=?.sub.0??, LT=T.sub.E?T.sub.S, the last expression can be rewritten as:

[00036]$\left(?\right)=\mathrm{FT}\left(f\left(t\right)\right)=e^{i{?}_{?}{T}_S}\frac{e^{i{?}_{?}LT}-1}{i{?}_{?}}=e^{i{?}_{?}{T}_S}*e^{\frac{i{?}_{?}LT}{2}}\left\{\frac{e^{\frac{i{?}_{?}LT}{2}}-e^{-\frac{i{?}_{?}LT}{2}}}{i{?}_{?}}\right\}=2*e^{i{?}_{?}{T}_S}*e^{\frac{i{?}_{?}LT}{2}}*\frac{\sin \frac{{?}_{?}LT}{2}}{{?}_{?}}=2*e^{\frac{i{?}_{?}{T}_C}{2}}*\frac{\sin \frac{{?}_{?}LT}{2}}{{?}_{?}},$$\mathrm{Here}:$$T_C=\frac{T_S+T_E}{2},\mathrm{LT}=T_E-T_S,{?}_{?}={?}_0-?$

[0247] The above expression allows us to deduce another useful formula for the FT of cos(wot) defined in the same interval t ? [T.sub.S,T.sub.E], as:

[00037]$\left(?\right)=FT\left(\cos \left({?}_{0}t\right)\right)=e^{i{?}_{?}^{-}{T}_C}*\frac{\sin \frac{{?}_{?}^{-}\mathrm{LT}}{2}}{{?}_{?}^{-}}+e^{-i{?}_{?}^{+}{T}_C}*\frac{\sin \frac{{?}_{?}^{-}\mathrm{LT}}{2}}{{?}_{?}^{-}}$$\mathrm{Here}:$$T_C=\frac{T_S+T_E}{2},\mathrm{LT}=T_E-T_S,{?}_{?}^{-}={?}_0-?,{?}_{?}^{+}={?}_0+?$

[0248] For the frequency ranges of our interest, we may stipulate:

[00038]$\frac{1}{{?}_{?}^{+}}?1$

[0249] As a result, the second term in the above FT formula is negligibly small (<10.sup.?6), and so for practical purposes one may use only the first term, as follows:

[00039]$\left(?\right)=FT\left(\cos \left({?}_{0}t\right)\right)=e^{i{?}_{?}^{-}{T}_C}*\frac{\sin \frac{{?}_{?}^{-}\mathrm{LT}}{2}}{{?}_{?}^{-}}$

When T.sub.C=0, the above formula gives us the very well know sinc-function, that has the value of LT/2 at ?=?.sub.0. The above formula for a signal with an initial phase ? and an amplitude A.sub.?.sub.0 transforms into:

[00040]$\begin{array}{cc}\begin{array}{c}\left(?\right)=\mathrm{FT}\left(A_{{?}_0}*\cos \left({?}_{0}t+?\right)\right)=A_{{?}_0}*e^{i?}*e^{i{?}_{?}^{-}{T}_C}*\frac{\sin \frac{{?}_{?}^{-}\mathrm{LT}}{2}}{{?}_{?}^{-}}\\ =A_{{?}_0}*e^{i?}*e^{\frac{i\left({?}_0-?\right)\left(T_S+T_E\right)}{2}}*\frac{\sin \frac{\left({?}_0-?\right)\left(T_E-T_S\right)}{2}}{{?}_0-?}\end{array}& \left[2\right]\end{array}$

[0250] The above a general approximation of the FT of: A.sub.?.sub.0*cos(?.sub.0t+?). This formula allows us to obtain a value of: A.sub.?.sub.0*cos(?.sub.0t+?) at any given frequency ? of a Fourier spectrum. This, in turn, allows us to estimate contributions from nearby peaks.

A Simple Case

[0251] Assume that we have N ions. The signal from each ion is represented by a single harmonic at ?.sub.k, all ions are assumed to have the same phase (to simplify formulas, we assume ?=0, but this is not necessary as long as the phase is the same for all ions), all ions are assumed to exist from the beginning of the transient (T.sub.S=0) and do not die so that all ions have the same T.sub.E that is equal to the length of the transient. All following considerations are easily extended to a scenario where each ion's signal is represented by several harmonics. Then, the frequency spectrum of an ion oscillating at ?.sub.k is given by:

[00041]$\left(?\right)=A_{{?}_k}*e^{\frac{i\left({?}_k-?\right)T_E}{2}}*\frac{\sin \frac{\left({?}_k-?\right)T_E}{2}}{{?}_k-?}$

[0252] Comparing this formula with the system of equations [1], we can see that if ?.sub.k and T.sub.E are known and fixed, one can calculate all coefficients ? for a given frequency ?.sub.m. In other words, one may calculate the contribution factor, ?.sub.mk, of an ion oscillating at ?.sub.k to the spectral component corresponding to the ion oscillating at ?.sub.m, as follows:

[00042]${?}_{mk}=e^{\frac{i\left({?}_k-{?}_m\right)T_E}{2}}*\frac{\sin \frac{\left({?}_k-{?}_m\right)T_E}{2}}{{?}_k-{?}_m}$

[0253] The system becomes linear with respect to unknown A.sub.?.sub.k and may be solved. In other words, the A.sub.?.sub.k are the TP.sub.k (k=1 to N) we require from equation [1] above.

[0254] In practice, due to the noise in the input signal and, therefore, inaccurate estimates of 0P.sub.k in equations [1], it may be preferable to take spectral values at several points around each ion's peak at several harmonic frequencies and search for a combination of A.sub.?.sub.k that delivers the best fit on equation [1] (in terms of the least squares, for example).

Another Example

[0255] In some experiments an ion may be born in the middle of an image-charge current signal transient. These so-called secondary ions will have different and unknown values of T.sub.S, T.sub.E and ?. As can be seen from equation [2], the system becomes non-linear with respect to these new unknowns. The phase term:

[00043]$e^{i?}*e^{\frac{i\left({?}_0-?\right)\left(T_S+T_E\right)}{2}}$

in equation [2] does not have a unique solution. In other words, the same value of this term can be delivered by different combinations of ?, T.sub.S and T.sub.E. This reflects the fact that the FT spectrum shows which frequency components exist in the signal but does not identify when they appear or for how long they exist. There are known standard approaches to solving systems of non-linear equations, for example, the Levenberg-Marquardt method, which are readily available to the skilled person. However, this method requires that the minimization function has a non-zero second derivative in the region of minimization, and this condition may not be satisfied in all cases.

[0256] The inventors have found that a numerical approach may be used particularly successfully in which the unknown variables are varied within predefined ranges with by predefined step sizes.

[0257] For example, in general, the lifetime, LT, (LT=T.sub.E?T.sub.S) values may be varied by varying T.sub.E in the range of ?45 ms?T.sub.E?+45 ms around an estimated values of T.sub.E. This variation may be implemented in step sizes of about 1 ms. Of course, other ranges and/or step-sizes may be employed, if desired.

[0258] For example, in general, the amplitudes, A.sub.?.sub.0, may be varied in the range 0.80?A.sub.?.sub.0?1.20. This variation may be implemented in step sizes of about 0.01. For example, an amplitude value of 1 may correspond to a charge of 50e. Of course, other ranges and/or step-sizes may be employed, if desired.

[0259] At each step of variation, a sum of squares of differences between the measured values and the analytical (model) values is calculated. The combination of unknowns that delivers the minimal sum of squares of differences is accepted as the solution of equations [1].

REFERENCES

[0260] A number of publications are cited above in order to more fully describe and disclose the invention and the state of the art to which the invention pertains. Full citations for these references are provided below. The entirety of each of these references is incorporated herein. [0261] Jared O. Kafader, STORI Plots Enable Accurate Tracking of Individual Ion Signals; J. Am. Soc. Mass Spectrum (2019) 30: 2200-2203 [0262] High-Capacity Electrostatic Ion Trap with Mass Resolving Power Boosted by High-Order Harmonics: by Li Ding and Aleksandr Rusinov, Anal. Chem. 2019, 91, 12, 7595-7602. [0263] W. Shockley: Currents to Conductors Induced by a Moving Point Charge, Journal of Applied Physics 9, 635 (1938)] [0264] S. Ramo: Currents Induced by Electron Motion, Proceedings of the IRE, Volume 27, Issue 9, September 1939 [0265] WO02/103747 (A1) (Zajfman et al.) [0266] WO2012/116765 (A1) (Ding et al.)