ELECTROSTATIC INTERACTIONS IN THE IONIC AND VAN DER WAALS COMPLEXES, DIRECT APPROACH
Loading...
Date
1994
Authors
Journal Title
Journal ISSN
Volume Title
Publisher
Ohio State University
Abstract
The analysis of spectroscopic data is one way to construct molecular potential energy curve, but the result of such a construction is always limited to the part of the potential surface probed the observed transitions. In many cases a Morse potential closely approximates the real potential and is sufficient, for example, to estimate dissociation energies. But in the general case such an extrapolation should employ some long-range bounding model. Because spectroscopic data are not strongly affected by the inner-wall part of potential, Hamiltonian can be written as a sum of an expressed in terms of repulsion term and the attractive electrostatic interaction in terms of an empirically expressed in terms of the polarizabilities, hyperpolarizabilities, etc. However, this approach has problems if there is a need to treat exited states with unknown polarizabilities, if electrostatic interaction induces significant changes in the molecular electronic eigenfunctions, or if there are more then two molecules in the complex. A direct, not perturbation theory based, approach is formulated and tested on the spectroscopic data of simple ionic complexes.
Description
Author Institution: Laser Spectroscopy Facility, Department of Chemistry, The Ohio State University