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Anharmonicity of excited‐state potential surfaces: quantum chemical analysis and resonance Raman intensities
Author(s) -
Brouwer A. M.,
Svendsen C.,
Mortensen O. S.,
Wilbrandt R.
Publication year - 1998
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/(sici)1097-4555(199806)29:6<439::aid-jrs264>3.0.co;2-p
Subject(s) - anharmonicity , raman spectroscopy , excited state , quantum chemical , resonance (particle physics) , chemistry , atomic physics , quantum , nuclear magnetic resonance , molecular physics , physics , quantum mechanics , molecule , organic chemistry
The experimental absorption and resonance Raman spectra of the radical cation of N , N ‐dimethylpiperazine are interpreted on the basis of ab initio density functional calculations and wavepacket propagation techniques. In particular, properties of the excited electronic state active in the resonance transition are discussed. It is shown that the excited‐state potential energy surface of the radical cation is strongly anharmonic. The observed resonance Raman spectra and their interpretation using different approaches are discussed in relation to this anharmonicity. It is concluded that resonance Raman spectroscopy, in combination with quantum chemical calculations, is a valuable tool for obtaining information on possible anharmonicity of the excited‐state potential energy surface. © 1998 John Wiley & Sons, Ltd.