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.

Can the Resonance Raman Optical Activity Spectrum Display Sign Alternation?

GIOVANNINI, TOMMASO;CAPPELLI, Chiara
2016

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.
Settore CHIM/02 - Chimica Fisica
File in questo prodotto:
File Dimensione Formato  
acs.jpclett.6b01756.pdf

Accesso chiuso

Tipologia: Published version
Licenza: Non pubblico
Dimensione 550.24 kB
Formato Adobe PDF
550.24 kB Adobe PDF   Visualizza/Apri   Richiedi una copia

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11384/63241
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 19
  • ???jsp.display-item.citation.isi??? 19
social impact