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Vibrational spectroscopy of cluster ions: Two novel methods

Conference ·
OSTI ID:5926714

Two sensitive techniques are discussed for obtaining vibrational spectra of cluster ions. The first approach is to attach a H/sub 2/ molecule to the hydrated hydronium ions. Because the original goal was to study the hydrated hydronium ions, the attached H/sub 2/ is hoped to have only a small effect on the spectrum. After an O-H stretch of the cluster ion has been excited, it vibrationally predissociates, losing the H/sub 2/. By monitoring the dissociation product as a function of laser frequency, the absorption spectra of these H/sub 3/O/sup +/ . (H/sub 2/O)/sub n/ . H/sub 2/ (n = 1,2,3) ions have been found. The second approach is to detect the vibrationally excited H/sub 3/O/sup +/ . (H/sub 2/O)/sub n/ (n = 1,2,3) ions using an infrared multiphoton dissociation process. The procedure is to first excite from v = 0 to v = 1 in the O-H stretch using a tunable ir laser. We then make use of the fact that the density of states near v = 0 and v = 1 are very different, and the vibrationally excited ionic clusters, which contain many low frequency vibrations, are likely to be in the quasicontinuum region for the sequential excitation by a fixed frequency laser. This means that one can distinguish between ground state and vibrationally excited H/sub 3/O/sup +/ . (H/sub 2/O)/sub n/ by using a multiphoton dissociation (MPD) process to selectively dissociate the latter using a CO/sub 2/ laser. Once again, we monitor the dissociation product ion signal as a function of the excitation frequency of the first laser to get the absorption spectra of the H/sub 3/O/sup +/ . (H/sub 2/O)/sub n/ ions. 5 refs.

Research Organization:
Lawrence Berkeley Lab., CA (USA)
DOE Contract Number:
AC03-76SF00098
OSTI ID:
5926714
Report Number(s):
LBL-23842; CONF-8704211-1; ON: DE88000617
Resource Relation:
CAMS/NCR workshop on molecular and cluster beam science, Washington, DC, USA, 24 Apr 1987
Country of Publication:
United States
Language:
English