2014
DOI: 10.1063/1.4895534
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A general time-dependent route to Resonance-Raman spectroscopy including Franck-Condon, Herzberg-Teller and Duschinsky effects

Abstract: 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… Show more

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Cited by 56 publications
(91 citation statements)
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“…[75] Consistent with these findings,t he mosts ignificant, intense bands in the experimental RR spectrumo fu racil at frequencies highert han 1000 cm À1 have been identifieda sr ing stretches coupled to primarily C5ÀH11a nd C6ÀH12 bending modes at 1235 cm À1 ,aring stretchingb and at 1388 cm À1 ,a nd aC 5 =C6 stretching mode at 1623 cm À1 . [75] Interestingly,t he second most intense band in the experimental spectrum at 1664 cm À1 corresponds predominantly to aC 4 =O10 stretching mode, [75] which does not appear to be of any relevance for thep hoto- (30,26), and DMRG-SCF (18,23). Frequencies for the ground state are taken from our PBE0/augcc-pVTZcalculation and scaled by 0.9776 (frequenciesl ower than 1000 cm À1 )a nd 0.9568 (frequencies highert han 1000cm À1 ), see Ref.…”
Section: Resonance Raman Spectramentioning
confidence: 94%
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“…[75] Consistent with these findings,t he mosts ignificant, intense bands in the experimental RR spectrumo fu racil at frequencies highert han 1000 cm À1 have been identifieda sr ing stretches coupled to primarily C5ÀH11a nd C6ÀH12 bending modes at 1235 cm À1 ,aring stretchingb and at 1388 cm À1 ,a nd aC 5 =C6 stretching mode at 1623 cm À1 . [75] Interestingly,t he second most intense band in the experimental spectrum at 1664 cm À1 corresponds predominantly to aC 4 =O10 stretching mode, [75] which does not appear to be of any relevance for thep hoto- (30,26), and DMRG-SCF (18,23). Frequencies for the ground state are taken from our PBE0/augcc-pVTZcalculation and scaled by 0.9776 (frequenciesl ower than 1000 cm À1 )a nd 0.9568 (frequencies highert han 1000cm À1 ), see Ref.…”
Section: Resonance Raman Spectramentioning
confidence: 94%
“…The resulting CAS(18,23)c omprises the eight p/p*o rbitals( which have the largest s i (1) values), the lone-pair of the carbonyl C4=O10 oxygen (from which the excitation occurs in the n!p*S 1 state), six s/s*o rbitals corresponding to the skeleton C4=O10, C4ÀC5, C5ÀC6 bondinga nd anti-bonding orbitals (as indicated by I ij values > 0.01) as well as eight additional Rydberg-type orbitals. Although still yielding too high vertical excitation energies (see Ta ble 1), the excited-state gap D S 2 ÀS 1 for DMRG-SCF (18,23) is the smallest one (1). The line connecting two orbitals denotestheir mutual information value I ij where darker (from green to black) and thicker lines correspond to an increasing value of the mutual information.…”
Section: Methodsmentioning
confidence: 99%
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