標題: Rotational dynamics of solvated carbon dioxide studied by infrared, Raman, and time-resolved infrared spectroscopies and a molecular dynamics simulation
作者: Watanabe, Kaori
Okajima, Hajime
Kato, Takuya
Hamaguchi, Hiro-o
應用化學系
應用化學系分子科學碩博班
Department of Applied Chemistry
Institute of Molecular science
關鍵字: carbon compounds;infrared spectra;molecular dynamics method;Raman spectra;rotational states;solvent effects;spectral line broadening;time resolved spectra;vibrational states
公開日期: 7-一月-2012
摘要: Rotational dynamics of solvated carbon dioxide (CO(2)) has been studied. The infrared absorption band of the antisymmetric stretch mode in acetonitrile is found to show a non-Lorentzian band shape, suggesting a non-exponential decay of the vibrational and/or rotational correlation functions. A combined method of a molecular dynamics (MD) simulation and a quantum chemical calculation well reproduces the observed band shape. The analysis suggests that the band broadening is almost purely rotational, while the contribution from the vibrational dephasing is negligibly small. The non-exponential rotational correlation decay can be explained by a simple rotor model simulation, which can treat large angle rotations of a relatively small molecule. A polarized Raman study of the symmetric stretch mode in acetonitrile gives a rotational bandwidth consistent with that obtained from the infrared analysis. A sub-picosecond time-resolved infrared absorption anisotropy measurement of the antisymmetric stretch mode in ethanol also gives a decay rate that is consistent with the observed rotational bandwidths. (C) 2012 American Institute of Physics. [doi:10.1063/1.3671998]
URI: http://dx.doi.org/10.1063/1.3671998
http://hdl.handle.net/11536/15266
ISSN: 0021-9606
DOI: 10.1063/1.3671998
期刊: JOURNAL OF CHEMICAL PHYSICS
Volume: 136
Issue: 1
結束頁: 
顯示於類別:期刊論文


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  1. 000298967200028.pdf