title: Can the Resonance Raman Optical Activity Spectrum Display Sign Alternation?
abstract: The monosignate character of resonance Raman optical activity (RROA) spectra has been often taken as granted in experimental and computational approaches, on the basis of basic theoretical approximations only considering resonance with a single electronic state of the molecule and the scattering process to be governed by the Franck-Condon mechanism. We show in this letter for the first time that, by resorting to a fully quantum mechanical (QM) methodology able to take into account all terms entering the general definition of RROA, and which considers excited state interference and Herzberg-Teller effects, sign alternation and at the same time intensity enhancement in RROA spectra is obtained. Such features constitute an important milestone toward the exploration of RROA of a wide range of chiral biological molecules.
authors: Universidade Tecnológica Federal do Paraná , Rua Deputado Heitor de Alencar Furtado, 4900, 81280-340, Curitiba, Brazil.
authors: Luciano N
authors: LN
authors: Vidal
authors: Scuola Normale Superiore , Piazza dei Cavalieri 7, 56126 Pisa, Italy.
authors: Tommaso
authors: T
authors: Giovannini
authors: Scuola Normale Superiore , Piazza dei Cavalieri 7, 56126 Pisa, Italy.
authors: Chiara
authors: C
authors: Cappelli