Density functional studies of hydrogen-bonded systems II. Solvation of theH2O-CO complex by a nonpolar solvent

A dielectric continuum approach (SCIPCM) in the framework of density functi onal theory has been applied to study the structures, energetics and vibrat ional spectra of hydrogen-bonded H2O-CO and H2O-OC complexes in a non-polar solvent. The dielectric constants for Ar (1.63), Kr (1.83) and Xe (2.19) w ere used in order to mimic the low-temperature matrix isolation experiments . We have found that calculations which include a dielectric reaction field around the complexes are able to reproduce the experimentally observed spe ctral changes. The correction of the calculated interaction energy for the basis set superposition error is discussed in the framework of the self-con sistent reaction field approach. (C) 2001 Elsevier Science B.V. All rights reserved.