Computational Study of the Rovibrational Spectrum of (OCS)₂

Abstract

In this paper, we report a new intermolecular potential energy surface and rovibrational transition frequencies and line strengths computed for the OCS dimer. the potential is made by fitting energies obtained from explicitly correlated coupled-cluster calculations and fit using an interpolating moving least squares method. the rovibrational Schroedinger equation is solved with a symmetry-adapted Lanczos algorithm and an uncoupled product basis set. All four intermolecular coordinates are included in the calculation. on the potential energy surface we find, previously unknown, cross-shaped isomers and also polar and non-polar isomers. the associated wavefunctions and energy levels are presented. to identify polar and cross states we use both calculations of line strengths and vibrational parent analysis. Calculated rotational constants differ from their experimental counterparts by less than 0.001 cm -1.

Department(s)

Chemistry

Keywords and Phrases

Basis sets; Computational studies; Coupled-cluster calculations; Intermolecular potential energy surfaces; Interpolating moving least squares; Lanczos algorithm; Line strength; Non-polar; Rotational constants; Rovibrational spectrum; Rovibrational transitions; Potential energy surfaces; Quantum chemistry; Schrodinger equation; Isomers

International Standard Serial Number (ISSN)

0021-9606

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2012 American Institute of Physics (AIP), All rights reserved.

Publication Date

01 Apr 2012

Link to Full Text

Share

 
COinS