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American Chemical Society, The Journal of Physical Chemistry A, 8(110), p. 2807-2815, 2006

DOI: 10.1021/jp056443c

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Solvent Effects on Raman Optical Activity Spectra Calculated Using the Polarizable Continuum Model

Journal article published in 2006 by Magdalena Pecul, Ewa Lamparska, Chiara Cappelli, Luca Frediani, Kenneth Ruud ORCID
This paper was not found in any repository; the policy of its publisher is unknown or unclear.
This paper was not found in any repository; the policy of its publisher is unknown or unclear.

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Abstract

The integral equation formulation of the polarizable continuum model (IEFPCM) has been extended to the calculation of solvent effects on vibrational Raman optical activity spectra. Gauge-origin independence of the differential scattering intensities of right and left circularly polarized light is ensured through the use of London atomic orbitals. Density functional theory (DFT) calculations have been carried out for bromochlorofluoromethane, methyloxirane, and epichlorhydrin. The results indicate that solvent effects on the ROA differential scattering intensities can be substantial, and vary in sign and magnitude for different vibrational modes. It is demonstrated that both direct and indirect effects are important in determining the total solvent effects on the ROA differential scattering intensities. Local field effects are shown to be in general small, whereas electronic nonequilibrium solvation has a profound effect on the calculated solvent effects compared to an equilibrium solvation model. For molecules with several conformations, the changes in the relative stability of the different conformers also lead to noticeable changes in the ROA spectra.