Pleanry Lecture: Molecular Spectrometry PL5

New methods and instrumentation for simultaneous,

high-speed mass spectrometry
G. Hieftje1, S. Ray1, E. Dennis1, A. Graham1, and C. Enke2
1
Department of Chemistry, Indiana University, Bloomington IN 47405 USA
2
University of New Mexico, Albuquerque, NM 87131 USA

E-mail: Hieftje@indiana.edu

Rapid spectral-repetition rate, high spectral resolution, and simultaneous detection

are highly desirable in mass spectrometry; together, they provide better isotope-ratio
precision, elevated signal-to-noise ratios, improved chromatographic resolution, and
simplified spectral interpretation. In this presentation, new mass-spectrometric
instrument designs will be described that yield all these benefits. These designs are
all similar in configuration to a time-of-flight instrument, but differ in one important
way: they employ constant-momentum acceleration rather than the conventional
constant-energy acceleration.
One such design is embodied in a distance-of-flight mass spectrometer (DOFMS).
DOFMS can be understood most easily by comparing it to a time-of-flight mass
spectrometer (TOFMS). In TOFMS, all ions are given the same kinetic energy
(KE=0.5 mV2), so ions separate in a field-free region according to mass-to-charge
ratios and strike a distant detector in order of those mass-to-charge ratios. As a result,
the time-resolved detector output is the mass spectrum itself. In contrast, in DOFMS,
ions are all given the same momentum (M=mV), so again their velocities are mass-
dependent. However, before the lightest ion of interest exits the field-free region, the
ions are driven sideways onto a spatially selective detector or detector array, so each
position corresponds to a different mass-to-charge ratio. Consequently, detection is
truly simultaneous, masses are spatially separated and can be separately collected,
energy focus is improved, spectral resolution is enhanced, and no high-speed
electronics are needed.
The second kind of new mass spectrometer is based on TOFMS itself, but uses
constant-momentum rather than constant-energy acceleration. As in DOFMS, this
mode of operation yields better mass-spectral resolution, albeit here over a limited
mass range. In essence, the TOFMS can be viewed as being a DOFMS system with a
single detector channel. Moreover, because the enhanced resolution applies to only a
limited mass range, ions outside that range can be discarded, so the repetition rate of
ion-batch introduction can be raised, and sensitivity boosted. For maximal flexibility,
the new spectrometer can be operated alternately in a constant-energy mode for wide
mass-range detection, and “zoomed” to constant-momentum mode for greater
resolution and sensitivity for targeted mass regions.
The power of these new instruments will be illustrated with applications ranging
from elemental analysis to the separation and collection of biomolecules.

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