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Asymmetric structure for the excited S 1 state of 2,2′‐bipyridine evidenced by picosecond time‐resolved resonance raman experiments and ab initio calculation
Author(s) -
De Waele V.,
Buntinx G.,
Flament JP.,
Poizat O.
Publication year - 2005
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.20599
Subject(s) - raman spectroscopy , excited state , picosecond , ab initio , resonance (particle physics) , ab initio quantum chemistry methods , chemistry , excitation , molecular physics , singlet state , ground state , atomic physics , resonance raman spectroscopy , molecule , laser , physics , optics , quantum mechanics , organic chemistry
The combination of ab initio calculation using the CIS method and experimental vibrational data from picosecond time‐resolved Raman measurements leads to a confident picture of the structure of the lowest excited singlet state S 1 ( n π*) of 2,2′‐bipyridine. The calculated structure is asymmetric with two dissimilar pyridyl moieties. It can be understood as resulting from a confinement of the excitation in one of the pyridyl rings, breaking the initial ground‐state symmetry. The reliability of this structure is attested by good agreement between the derived theoretical vibrational data and the experimental Raman spectra. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005