Infrared multiphoton decomposition and energy-dependent absorption cross section of chloroethane

Joseph S. Francisco, Warren D. Lawrance, Jeffrey I. Steinfeld, Robert G. Gilbert

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

The results are presented of an investigation of the multiple infrared photon decomposition of chloroethane with radiation of wavelength ∼ 10 μm, which is absorbed by the C-C stretching mode of the molecule. The study employed a focussed beam of maximum fluence 190 J/cm2. The fluence dependence of the fractional decomposition with ṽ = 966 cm-1 radiation under nearly collision-free conditions (0.035 torr) was quantitatively interpreted by solution of the appropriate master equation (taking postpulse collisions into account) to obtain the energy-dependent absorption cross section, σ(E). It was found that decomposition at high fluence (arising from energies in the range 19000-28000 cm-1) and energy absorption at low fluence (mean absorbed energy ∼ 150-1000 cm-1) could be simultaneously fitted with σ(E)/cm2 = 2.5 × 10-19 exp[-3.45(E/hv)0.14]. Comparison of this dependence with that found from data obtained with ṽ ∼ 2700 cm-1 suggests that the oscillator strength is strongly dependent on the mode being excited, even when the energy is thoroughly randomized within the molecule.

Original languageEnglish
Pages (from-to)724-728
Number of pages5
JournalJournal of Physical Chemistry
Volume86
Issue number5
DOIs
Publication statusPublished - 1982
Externally publishedYes

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