An apparatus 41 and operation method are provided for an electrostatic trap mass spectrometer with measuring frequency of multiple isochronous ionic oscillations. For improving throughput and space charge capacity, the trap is substantially extended in one Z-direction forming a reproduced two-dimensional field. Multiple geometries are provided for trap Z-extension. The throughput of the analysis is improved by multiplexing electrostatic traps. The frequency analysis is accelerated by the shortening of ion packets and either by Wavelet-fit analysis of the image current signal or by using a time-of-flight detector for sampling a small portion of ions per oscillation. Multiple pulsed converters are suggested for optimal ion injection into electrostatic traps.

A multi-reflection mass spectrometer is provided comprising two ion-optical mirrors, each mirror elongated generally along a drift direction (Y), each mirror opposing the other in an X direction, the X direction being orthogonal to Y, characterized in that the mirrors are not a constant distance from each other in the X direction along at least a portion of their lengths in the drift direction. In use, ions are reflected from one opposing mirror to the other a plurality of times while drifting along the drift direction so as to follow a generally zigzag path within the mass spectrometer. The motion of ions along the drift direction is opposed by an electric field resulting from the non-constant distance of the mirrors from each other along at least a portion of their lengths in the drift direction that causes the ions to reverse their direction.

An electrostatic trap such as an orbitrap is disclosed, with an electrode structure. An electrostatic trapping field of the form U(r, ?, z) is generated to trap ions within the trap so that they undergo isochronous oscillations. The trapping field U(r, ?, z) is the result of a perturbation W to an ideal field U(r, ?, z) which, for example, is hyperlogarithmic in the case of an orbitrap. The perturbation W may be introduced in various ways, such as by distorting the geometry of the trap so that it no longer follows an equipotential of the ideal field U(r, ?, z), or by adding a distortion field (either electric or magnetic). The magnitude of the perturbation is such that at least some of the trapped ions have an absolute phase spread of more than zero but less than 2 ? radians over an ion detection period T.sub.m.

Method and embodiments are provided for tandem mass spectrometer designed for extremely large charge throughput up to 1E+10 ion/sec. In one operation mode, the initial ion flow with wide m/z range is time separated in a trap array. The array ejects ions with a narrower momentarily m/z range. Ion flow is collected and confined in a wide bore ion channel at a limited time spread. The ion flow with narrow m/z range is then analyzed in a multi-reflecting TOF at frequent and time-encoded operation of the orthogonal accelerator, thus forming multiple non overlapping spectral segments. In another mode, time separated ions are subjected to fragmentation for comprehensive, all-mass MS-MS analysis. The momentarily ion flow at MR-TOF entrance is characterized by lower spectral population which allows efficient decoding of overlapping spectra. Those modes are combined with conventional spectrometer operation to improve the dynamic range. To provide practical solution, there are proposed multiple novel components comprising trap arrays, wide bore confining channels, resistive multipole, so as long life TOF detector.

A method for analyzing ions according to their mass-to-charge ratio and mass spectrometer for performing the method, comprising directing a collimated ion beam along an ion path from an ion source to an ion detector, causing a portion of the ion beam to contact one or more surfaces prior to reaching the ion detector, wherein the method comprises providing a coating on and/or heating the one or more surfaces to reduce variation in their surface patch potentials. The method is applicable to multi-reflection time-of-flight (MR TOF) mass spectrometry.

A multi-reflecting time-of-flight mass spectrometer comprises a pair of parallel aligned ion mirrors and a set of periodic lenses for confining ion packets along the drift z-direction. To compensate for time-of-flight spherical aberrations T|zz created by the periodic lenses, at least one set of electrodes are disposed within the apparatus, forming an accelerating or reflecting electrostatic fields which are curved in the z-direction in order to form local negative T|zz aberration. The structure may be formed within an accelerator, within flinging fields or intentionally and locally curved fields of ion mirrors, within electrostatic sector interface, or at curved surface of ion to electron converter at the detector.

A time-of-flight mass spectrometer is disclosed comprising: an ion deflector (305) configured to deflect ions to different positions in a first array of positions at different times; a position sensitive ion detector (187); and ion optics (180) arranged and configured to guide ions from the first array of positions to the position sensitive detector (187) so as to map ions from the first array of positions to a second array of positions on the position sensitive detector (187); wherein the ion optics includes at least one ion mirror for reflecting the ions.

A mass spectrometer comprising: a pulsed ion source for generating pulses of ions having a range of masses; a time-of-flight mass analyzer for receiving and mass analyzing the pulses of ions from the ion source; and an energy controlling electrode assembly located between the pulsed ion source and the time-of-flight mass analyzer configured to receive the pulses of ions from the pulsed ion source and apply a time-dependent potential to the ions thereby to control the energy of the ions depending on their m/z before they reach the time-of-flight mass analyzer. Mass dependent differences in average energy of ions can be reduced for injection into a time-of-flight mass analyzer, which can improve ion transmission and/or instrument resolving power.

An ion mirror is disclosed comprising an ion entrance electrode section (62) at the ion entrance to the ion mirror, an energy focussing electrode section (66) for reflecting ions back along a longitudinal axis towards said ion entrance, and a spatial focussing electrode section (64) arranged between the ion entrance electrode section (62) and the energy focussing electrode section (66) for spatially focussing the ions. One or more DC voltage supply is provided to apply a DC potential to the ion entrance electrode section (62) that is intermediate the DC potential applied to the spatial focussing electrode section (64) and the DC potential applied to the energy focussing electrode section (66). The ion mirror further comprises: (i) at least one first transition electrode (68) arranged between said ion entrance electrode section (62) and said spatial focussing electrode section (64), wherein said one or more DC voltage supply is configured to apply a DC potential to said at least one first transition electrode that is intermediate the DC potential applied to the ion entrance electrode section (62) and the DC potential applied to the spatial focussing electrode section (64); and (ii) at least one second transition electrode (69) arranged between said energy focussing electrode section (66) and said spatial focussing electrode section (64), wherein said one or more DC voltage supply is configured to apply a DC potential to said at least one second transition electrode (69) that is intermediate the DC potential applied to the spatial focussing electrode section (64) and the DC potential applied to the ion entrance electrode section (62).

An apparatus 41 and operation method are provided for an electrostatic trap mass spectrometer with measuring frequency of multiple isochronous ionic oscillations. For improving throughput and space charge capacity, the trap is substantially extended in one Z-direction forming a reproduced two-dimensional field. Multiple geometries are provided for trap Z-extension. The throughput of the analysis is improved by multiplexing electrostatic traps. The frequency analysis is accelerated by the shortening of ion packets and either by Wavelet-fit analysis of the image current signal or by using a time-of-flight detector for sampling a small portion of ions per oscillation. Multiple pulsed converters are suggested for optimal ion injection into electrostatic traps.