Effect of Secondary Basis-Set Superposition Error Upon Calculated Vibrational Intensities

Authors

M. M. Szczesniak, Southern Illinois University
Steve Scheiner, Southern Illinois UniversityFollow

Document Type

Article

Journal/Book Title/Conference

Chemical Physics Letters

Volume

131

Issue

3

Publisher

Elsevier BV

Publication Date

11-1-1986

First Page

230

Last Page

236

Abstract

The calculated dipole movement and polarizability of a molecule are affected by the position of the ghost orbitais of its partner subunit within a molecular complex. The IR and Raman intensities, evaluated in terms of the derivatives of these properties with respect to an intermolecular motion, are hence subject to a secondary basis-set superposition error (BSSE), here calculated for (HF)₂ with a variety of basis sets. Whereas the IR intensity is only slightly affected, the BSSE introduces enormous errors into the Raman intensities. These errors can be reduced if two sets of polarization functions are included in the basis set.

Recommended Citation

M.M. Szczesniak, Steve Scheiner, Effect of secondary basis-set superposition error upon calculated vibrational intensities, Chemical Physics Letters, Volume 131, Issue 3, 1986, Pages 230-236, ISSN 0009-2614, https://doi.org/10.1016/0009-2614(86)80551-6.