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Title: A general time-dependent route to Resonance-Raman spectroscopy including Franck-Condon, Herzberg-Teller and Duschinsky effects

We present a new formulation of the time-dependent theory of Resonance-Raman spectroscopy (TD-RR). Particular attention has been devoted to the generality of the framework and to the possibility of including different effects (Duschinsky mixing, Herzberg-Teller contributions). Furthermore, the effects of different harmonic models for the intermediate electronic state are also investigated. Thanks to the implementation of the TD-RR procedure within a general-purpose quantum-chemistry program, both solvation and leading anharmonicity effects have been included in an effective way. The reliability and stability of our TD-RR implementation are validated against our previously proposed and well-tested time-independent procedure. Practical applications are illustrated with some closed- and open-shell medium-size molecules (anthracene, phenoxyl radical, benzyl radical) and the simulated spectra are compared to the experimental results. More complex and larger systems, not limited to organic compounds, can be also studied, as shown for the case of Tris(bipyridine)ruthenium(II) chloride.
Authors:
;  [1] ;  [1] ;  [2]
  1. Scuola Normale Superiore, piazza dei Cavalieri 7, I-56126 Pisa (Italy)
  2. (ICCOM-CNR), UOS di Pisa, Area della Ricerca CNR, Via G. Moruzzi 1, I-56124 Pisa (Italy)
Publication Date:
OSTI Identifier:
22308399
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 11; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANTHRACENE; BENZYL RADICALS; BIPYRIDINES; MOLECULES; RAMAN SPECTROSCOPY; RESONANCE; RUTHENIUM CHLORIDES; SIMULATION; SOLVATION; SPECTRA