title: A robust and effective time-independent route to the calculation of Resonance Raman spectra of large molecules in condensed phases with the inclusion of Duschinsky, Herzberg-Teller, anharmonic, and environmental effects.
abstract: We present an effective time-independent implementation to model vibrational resonance Raman (RR) spectra of medium-large molecular systems with the inclusion of Franck-Condon (FC) and Herzberg-Teller (HT) effects and a full account of the possible differences between the harmonic potential energy surfaces of the ground and resonant electronic states. Thanks to a number of algorithmic improvements and very effective parallelization, the full computations of fundamentals, overtones, and combination bands can be routinely performed for large systems possibly involving more than two electronic states. In order to improve the accuracy of the results, an effective inclusion of the leading anharmonic effects is also possible, together with environmental contributions under different solvation regimes. Reduced-dimensionality approaches can further enlarge the range of applications of this new tool. Applications to imidazole, pyrene, and chlorophylla1 in solution are reported, as well as comparisons with available experimental data.
authors.affiliation: Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126 Pisa, Italy.
authors.forename: Franco
authors.initials: F
authors.lastname: Egidi
authors.affiliation: Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126 Pisa, Italy ; Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti Organometallici, UOS di Pisa, Via G. Moruzzi 1, 56124 Pisa, Italy.
authors.forename: Julien
authors.initials: J
authors.lastname: Bloino
authors.affiliation: Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via Risorgimento 35, 56126 Pisa, Italy.
authors.forename: Chiara
authors.initials: C
authors.lastname: Cappelli
authors.affiliation: Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126 Pisa, Italy.
authors.forename: Vincenzo
authors.initials: V
authors.lastname: Barone