AB INITIO CALCULATION OF THE VIBRATIONAL STRUCTURE OF PHOTOELECTRON SPECTRA FOR FREE RADICALS
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Date
1994
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Ohio State University
Abstract
Ab initio calculations, mostly by means of the CEPA-1 $method,^{1}$ were carried out for radicals and cation of type $CX_{n} Y_{3-n}$ with $X,Y = F, $Cl. Most emphasis is given to the vibrational structure of the first band of the photoelectron (PE) spectra. Due to strong mode coupling these are rather complex. Already the low-temperature PE spectrum of $CCl_{3}$, which may be well described as a two-mode problem, shows more than 100 lines with more than 1% relative intensity in the range $0--10000 cm^{-1}$. Several of the vibrational frequencies of the cations may be compared with experimental data from matrix-isolation IR spectroscopy;$^{2}$ throughout the agreement is very good.
Description
$^{1}$ CEPA-1: Coupled Electron Pair Approximation, version 1; W. Meyer, J. Chem. Phys. 58, 1017 (1973). $^{2}$ M. E. Jacox, J. Phys. Chem. Ref. Data, 13 (1984), and reference therein.
Author Institution: Institute f\""{u}r Physikalische Chemie, der Universit\""{a}t G\""{o}ttingen
Author Institution: Institute f\""{u}r Physikalische Chemie, der Universit\""{a}t G\""{o}ttingen