Journal of Physical Chemistry, Vol.99, No.43, 15758-15764, 1995
Solvent Effects on Optical-Emission and Absorption-Spectra - Theoretical Calculation of the (1)(N, Pi-Asterisk) Transition of Formaldehyde in Solution
A nonequilibrium polarizable continuum model, proposed in a previous paper (J. Chem. Phys. 1993, 98, 7375), is applied to the study, at CIS and CISD levels, of solvent effects on the electronic structure of the (1)(n, pi*) transition of formaldehyde. To obtain a proper description of the excited state properties in solution, the generalized density matrix must be employed. The effects of the electrostatic dielectric potential, dispersion, and the Stark term, as well as the specific solute-solvent interaction are analyzed. The contribution to the solvent shift from the dispersion component is of comparatively minor importance in the absorption process, but constitutes an appreciable fraction of the total shift in the emission process. The contribution of the Stark effect term is very small and may be neglected. Explicit addition of water molecules to the carbonyl compound is necessary to account for the observed blue shift.
Keywords:PI-ASTERISK TRANSITION;NONEQUILIBRIUM SOLVATION;ELECTRONIC-STRUCTURE;SOLVATOCHROMIC SHIFTS;ABINITIO EVALUATION;WATER COMPLEXES;BLUE SHIFT;CONTINUUM;ENERGY;SIMULATION