Towards an accurate description of anharmonic infrared spectra in solution within the polarizable continuum model: Reaction field, cavity field and nonequilibrium effects
Abstract
We present a newly developed and implemented methodology to perturbatively evaluate anharmonic vibrational frequencies and infrared (IR) intensities of solvated systems described by means of the polarizable continuum model (PCM). The essential aspects of the theoretical model and of the implementation are described and some numerical tests are shown, with special emphasis towards the evaluation of IR intensities, for which the quality of the present method is compared to other methodologies widely used in the literature. Proper account of an incomplete solvation regime in the treatment of the molecular vibration is also considered, as well as inclusion of the coupling between the solvent and the probing field (cavity field effects). In order to assess the quality of our approach, comparison with experimental findings is reported for selected cases.
- Publication:
-
Journal of Chemical Physics
- Pub Date:
- September 2011
- DOI:
- 10.1063/1.3630920
- Bibcode:
- 2011JChPh.135j4505C
- Keywords:
-
- infrared spectra;
- liquid theory;
- perturbation theory;
- solvation;
- vibrational modes;
- 78.30.cd;
- 61.20.Gy;
- 82.30.Nr;
- 63.50.-x;
- Theory and models of liquid structure;
- Association addition insertion cluster formation;
- Vibrational states in disordered systems