Voth, Gregory A. and Marcus, R. A. and Zewail, A. H. (1984) The highly excited C-H stretching states of CHD_3, CHT_3, and CH_3D. Journal of Chemical Physics, 81 (12). pp. 5494-5507. ISSN 0021-9606 http://resolver.caltech.edu/CaltechAUTHORS:20120703-093554866
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Unlike many other molecules having local modes, the highly excited C-H stretching states of CHD_3 show well resolved experimental spectra and simple Fermi resonance behavior. In this paper the local mode features in this prototype molecule are examined using a curvilinear coordinate approach. Theory and experiment are used to identify the vibrational state coupling. Both kinetic and potential terms are employed in order to characterize the coupling of the C-H stretch to various other vibrational modes, notably those including D-C-H bending. Predictions are also made for CHT_3 and the role of dynamical coupling on the vibrational states of CH_3D explored. Implications of these findings for mode-specific and other couplings are discussed.
|Additional Information:||© 1984 American Institute of Physics. Received 9 July 1984; accepted 11 September 1984. This work is supported by grants from the National Science Foundation. We would like to thank Dr. J. W. Perry for many helpful discussions on the experimental and theoretical aspects of this work and Dr. A. G. Robiette for information on the various coordinate systems used in our calculations.|
|Subject Keywords:||methane; deuterium; tritium; vibrational states; coupling; oscillation modes; excited states; isotope effects; fermi resonance|
|Other Numbering System:|
|Classification Code:||PACS: 33.20.Tp; 31.50.Df; 33.20.Ea|
|Official Citation:||The highly excited C--H stretching states of CHD[sub 3], CHT[sub 3], and CH[sub 3]D Gregory A. Voth, R. A. Marcus, and A. H. Zewail, J. Chem. Phys. 81, 5494 (1984), DOI:10.1063/1.447650|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Aucoeur Ngo|
|Deposited On:||03 Jul 2012 18:15|
|Last Modified:||26 Dec 2012 15:27|
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