De. Goeringer et Sa. Mcluckey, RELAXATION OF INTERNALLY EXCITED HIGH-MASS IONS SIMULATED UNDER TYPICAL QUADRUPOLE ION-TRAP STORAGE-CONDITIONS, International journal of mass spectrometry and ion processes, 177(2-3), 1998, pp. 163-174
Citations number
55
Categorie Soggetti
Spectroscopy,"Physics, Atomic, Molecular & Chemical
Collisional relaxation of internally excited high-mass (>1 kDa) ions h
as been simulated under typical quadrupole ion trap storage conditions
. Two models have been employed that are expected to bracket the range
of cooling rates that prevail for such ions present in similar to 1 m
Torr of room temperature helium. A diffuse scattering model that assum
es that the helium target atom thermally equilibrates with the high-ma
ss ion upon collision is expected to yield a maximum cooling rate. A r
andom walk algorithm using the exponential model for inefficient colli
ders and a relatively small average energy down-step size provides an
estimate for the lowest cooling rates that might be expected. The two
models give cooling rates that differ by about a factor of three and f
all within the range of 200-2000 s(-1) for the ions and energies consi
dered in the simulations. Unimolecular dissociation rates have also be
en determined for the same model ions. Random wall simulations employi
ng collisional cooling and dissociation clearly show how a rapid input
of internal energy, as with the absorption of an ultraviolet photon,
can either result in dissociation of a large fraction of the ions or c
an lead to an insignificant degree of dissociation, depending largely
on the unimolecular dissociation rate of the ion. (Int J Mass Spectrom
177 (1998) 163-174) (C) 1998 Elsevier Science B.V.