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Picosecond Vibrational Spectroscopy of Intermolecular Energy Transfer and Overtone Relaxation in Liquid Bromoform
Author(s) -
Seifert G.,
Patzlaff T.,
Graener H.
Publication year - 2000
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.200000090
Subject(s) - bromoform , overtone , chemistry , intermolecular force , picosecond , vibrational energy relaxation , raman spectroscopy , spectroscopy , relaxation (psychology) , analytical chemistry (journal) , molecule , spectral line , organic chemistry , optics , laser , psychology , social psychology , physics , quantum mechanics , astronomy , chloroform
Intermolecular energy transfer in liquid bromoform and d‐bromoform was investigated by help of picosecond IR and Raman spectroscopy. For a comprehensive interpretation of the corresponding results the study of C‐H bending overtone (2v 4 ) relaxation was necessary; the effective vibrational lifetime of this vibrational mode was determined to T 1 = 3±1 ps. For the intermolecular transfer a dominating process between the intramolecularly equilibrated C‐Br stretching modes v 2 and v 5 of CHBr 3 and CDBr 3 with a rate constant of 4·10 10 s −1 was recognized. Other possible channels, particularly the one between the quasi resonant modes v 1 (C‐D) and 2v 4 (C‐H) were found to be negligible.