C. Cappelli et al., Nonequilibrium formulation of infrared frequencies and intensities in solution: Analytical evaluation within the polarizable continuum model, J CHEM PHYS, 113(24), 2000, pp. 11270-11279
We present a nonequilibrium approach to the analytical evaluation of infrar
ed frequencies and intensities for molecules in solution within the polariz
able continuum model framework. Vibrational frequencies and intensities are
obtained in the harmonic approximation as the second derivatives of the su
itable nonequilibrium free energy. A numerical application to the calculati
on of carbonyl stretching frequencies and intensities of a series of ketone
s at the density functional level is shown. In order to effectively compare
theoretical and experimental data the coupling between the solvent and the
probing field is also taken into account. The dependence of the results on
the choice of the functional and of the basis set, as well as on the cavit
y geometry, is considered. (C) 2000 American Institute of Physics. [S0021-9
606(00)51948-5].