C–H local modes in cyclobutene. II. Laser photoacoustic studies 10 000–17 000 cm−1. Vibrational structure and C–H local mode dynamics

Baggott, J. E., Law, D. W., Lightfoot, P. D. and Mills, I. (1986) C–H local modes in cyclobutene. II. Laser photoacoustic studies 10 000–17 000 cm−1. Vibrational structure and C–H local mode dynamics. The Journal of Chemical Physics, 85 (10). pp. 5414-5429. ISSN 0021-9606 doi: 10.1063/1.451606

Abstract/Summary

In part I of this study [Baggott, Clase, and Mills, Spectrochim. Acta Part A 42, 319 (1986)] we presented FTIR spectra of gas phase cyclobutene and modeled the v=1–3 stretching states of both olefinic and methylenic C–H bonds in terms of a local mode model. In this paper we present some improvements to our original model and make use of recently derived ‘‘x,K relations’’ to find the equivalent normal mode descriptions. The use of both the local mode and normal mode approaches to modeling the vibrational structure is described in some detail. We present evidence for Fermi resonance interactions between the methylenic C–H stretch overtones and ring C–C stretch vibrations, revealed in laser photoacoustic spectra in the v=4–6 region. An approximate model vibrational Hamiltonian is proposed to explain the observed structure and is used to calculate the dynamics of the C–H stretch local mode decay resulting from interaction with lower frequency ring modes. The implications of our experimental and theoretical studies for mode‐selective photochemistry are discussed briefly.