A methodology for the theoretical evaluation of vibrational Raman scattering intensities for molecules in solution in the polarizable continuum model (PCM) framework is presented. Raman intensities are expressed in terms of derivatives of the dynamic effective polarizability with respect to nuclear coordinates. Local field effects are included by considering both the solvent polarization induced by the probing field (cavity field) and the solvent reaction field. The dependence of computed Raman intensities on the parameters of the calculation (basis set, exchange-correlation functional for DFT calculations, and cavity size) is discussed. A comparison between PCM and semiclassical values for simple molecules in various solvents is made.

Theoretical approach to the calculation of vibrational Raman spectra in solution within the Polarizable Continuum Model

CAPPELLI, Chiara;
2001

Abstract

A methodology for the theoretical evaluation of vibrational Raman scattering intensities for molecules in solution in the polarizable continuum model (PCM) framework is presented. Raman intensities are expressed in terms of derivatives of the dynamic effective polarizability with respect to nuclear coordinates. Local field effects are included by considering both the solvent polarization induced by the probing field (cavity field) and the solvent reaction field. The dependence of computed Raman intensities on the parameters of the calculation (basis set, exchange-correlation functional for DFT calculations, and cavity size) is discussed. A comparison between PCM and semiclassical values for simple molecules in various solvents is made.
File in questo prodotto:
Non ci sono file associati a questo prodotto.

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/11384/59412
 Attenzione

Attenzione! I dati visualizzati non sono stati sottoposti a validazione da parte dell'ateneo

Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 53
  • ???jsp.display-item.citation.isi??? 49
social impact