PMID: 11605273Oct 19, 2001Paper

Fluorescence-dip IR spectra of jet-cooled benzoic acid dimer in its ground and first excited singlet states

Faraday Discussions
G M FlorioT S Zwier

Abstract

The IR spectra of three isotopomers of the benzoic acid dimer have been recorded under jet-cooled conditions using the double resonance method of fluorescence-dip IR spectroscopy. In so doing, the spectra are assuredly due exclusively to dimers in the ground-state zero-point level at a rotational temperature of 3-5 K. Even under these conditions, the three isotopomers have remarkably broad spectra, extending from 2600 to almost 3150 cm-1. The spectra show extensive substructure consisting of some 15-20 transitions where only a single OH stretch fundamental should appear in the harmonic limit. The comparison of the undeuterated d0-d0 dimer with the ring-deuterated d5-d5 dimer tests the effect of mixing with the C-H stretches and overtones of the C-H bends. The mixed OH/OD ring-deuterated d6-d5 dimer shifts the frequency and changes the form of the OH stretch normal mode. The analogous OH stretch IR spectrum of the d0-d0 dimer out of the S1 excited-state zero-point level has also been recorded. In this case, much of the closely-spaced substructure is not apparent. What remains is a set of three bands separated from one another by about 180 cm-1. Preliminary results of model calculations of the anharmonic coupling, responsible for...Continue Reading

Citations

Jul 23, 2005·The Journal of Chemical Physics·Erika L DerroMarsha I Lester
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