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Ultrafast vibrational dynamics and solvation complexes of methyl acetate in methanol studied by sub‐picosecond infrared spectroscopy
Author(s) -
Banno Motohiro,
Ohta Kaoru,
Tominaga Keisuke
Publication year - 2008
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.2065
Subject(s) - intramolecular force , chemistry , solvation , vibrational energy relaxation , hydrogen bond , infrared spectroscopy , picosecond , raman spectroscopy , intermolecular force , methanol , infrared , monomer , molecular vibration , solvent , spectroscopy , photochemistry , analytical chemistry (journal) , molecule , stereochemistry , organic chemistry , laser , physics , quantum mechanics , optics , polymer
The vibrational dynamics of the CO stretching mode of methyl acetate (MA) in methanol was studied by time‐resolved infrared (IR) pump‐probe spectroscopy. The vibrational energy relaxation (VER) process includes two components with time constants of 1.3 ± 0.1 and 4.0 ± 0.2 ps. These components result from the vibrational excitations of the hydrogen‐bonding complex of MA with one methanol and the MA monomer, respectively. The difference in the VER time is explained by the increase of the vibrational density of states (VDOS) by the intermolecular hydrogen bond. The time constants and the decay‐associated spectra are almost identical between the CH 3 OH and the CH 3 OD solutions. The vibrational modes localized in the intramolecular OH/OD bond of the solvent methanol have little effect on the vibrational dynamics of MA. Copyright © 2008 John Wiley & Sons, Ltd.