Explicitly correlated coupled cluster calculations for molecules containing group 11 (Cu, Ag, Au) and 12 (Zn, Cd, Hg) elements: optimized complementary auxiliary basis sets for valence and core–valence basis sets

Hill, J.G. and Peterson, K.A. (2012) Explicitly correlated coupled cluster calculations for molecules containing group 11 (Cu, Ag, Au) and 12 (Zn, Cd, Hg) elements: optimized complementary auxiliary basis sets for valence and core–valence basis sets. Journal of Chemical Theory and Computation, 8(2), pp. 518-526. (doi: 10.1021/ct200856f)

Full text not currently available from Enlighten.

Abstract

Compact auxiliary basis sets matched to the standard aug-cc-pVnZ-PP and aug-cc-pwCVnZ-PP orbital basis sets have been developed for the coinage metals (Cu, Ag, Au) and group 12 elements (Zn, Cd, Hg) for use in the resolution of the identity (RI) approximation in explicitly correlated F12 calculations. The CCSD(T)-F12b method has been utilized with these auxiliary basis sets to carry out molecular benchmark calculations on homonuclear coinage metal diatomics (Cu<sub>2</sub>, Ag<sub>2</sub>, Au<sub>2</sub>), as well as mono- (CuF, AgF, AuF) and difluorides (CuF<sub>2</sub>, AgF<sub>2</sub>, AuF<sub>2</sub>). The resulting equilibrium geometries, harmonic vibrational frequencies, and atomization energies demonstrate that CCSD(T)-F12b calculations using double-ζ-quality basis sets produce results comparable in accuracy to conventional CCSD(T) quadruple-ζ calculations, while F12b with triple-ζ-quality sets yields results close to 5-ζ, which is near the conventional complete basis set (CBS) limit estimates. Analogous trends are observed for the group 12 monofluorides (ZnF, CdF, HgF). It is also shown that the effects of correlating the transition metal element (n – 1)s and p electrons are relatively insensitive to the size of the basis set when the F12 method is utilized.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Hill, Dr John
Authors: Hill, J.G., and Peterson, K.A.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of Chemical Theory and Computation
Publisher:American Chemical Society
ISSN:1549-9618
Published Online:19 January 2012

University Staff: Request a correction | Enlighten Editors: Update this record