Published in

American Institute of Physics, The Journal of Chemical Physics, 7(135), p. 074302

DOI: 10.1063/1.3624570

Links

Tools

Export citation

Search in Google Scholar

High-level ab initio potential energy surfaces and vibrational energies of H2CS

Journal article published in 2011 by Andrey Yachmenev, Sn Yurchenko ORCID, Tristan Ribeyre, Walter Thiel ORCID
This paper is available in a repository.
This paper is available in a repository.

Full text: Download

Green circle
Preprint: archiving allowed
Green circle
Postprint: archiving allowed
Orange circle
Published version: archiving restricted
Data provided by SHERPA/RoMEO

Abstract

Six-dimensional (6D) potential energy surfaces (PESs) of H2CS have been generated ab initio using the recently proposed explicitly correlated (F12) singles and doubles coupled cluster method including a perturbational estimate of connected triple excitations, CCSD(T)-F12b [T. B. Adler, G. Knizia, and H.-J. Werner, J. Chem. Phys. 127, 221106 (2007)] in conjunction with F12-optimized correlation consistent basis sets. Core-electron correlation, high-order correlation, scalar relativistic, and diagonal Born-Oppenheimer terms were included as additive high-level (HL) corrections. The resulting 6D PESs were represented by analytical functions which were used in variational calculations of the vibrational term values below 5000 cm(-1). The best PESs obtained with and without the HL corrections, VQZ-F12*(HL) and VQZ-F12*, reproduce the fundamental vibrational wavenumbers with mean absolute deviations of 1.13 and 1.22 cm(-1), respectively. A detailed analysis of the effects of the HL corrections shows how the VQZ-F12 results benefit from error cancellation. The present purely ab initio PESs will be useful as starting points for empirical refinements towards an accurate "spectroscopic" PES of H2CS. (C) 2011 American Institute of Physics. [doi:10.1063/1.3624570]