Tailored coupled cluster singles and doubles method applied to calculations on molecular structure and harmonic vibrational frequencies of ozone

Osamu Hino; Tomoko Kinoshita; Garnet Kin-Lic Chan; Rodney J Bartlett

doi:10.1063/1.2180775

Tailored coupled cluster singles and doubles method applied to calculations on molecular structure and harmonic vibrational frequencies of ozone

J Chem Phys. 2006 Mar 21;124(11):114311. doi: 10.1063/1.2180775.

Authors

Osamu Hino¹, Tomoko Kinoshita, Garnet Kin-Lic Chan, Rodney J Bartlett

Affiliation

¹ Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853-1301, USA. oh32@cornell.edu

PMID: 16555892
DOI: 10.1063/1.2180775

Abstract

To assess the separation of dynamic and nondynamic correlations and orbital choice, we calculate the molecular structure and harmonic vibrational frequencies of ozone with the recently developed tailored coupled cluster singles and doubles method (TCCSD). We employ the Hartree-Fock and complete active space (CAS) self-consistent field (SCF) orbitals to perform TCCSD calculations. When using the Hartree-Fock orbitals, it is difficult to reproduce the experimental vibrational frequency of the asymmetric stretching mode. On the other hand, the TCCSD based on the CASSCF orbitals in a correlation consistent polarized valence triple zeta basis yields excellent results with the two symmetric vibrations differing from the experimental harmonic values by 2 cm(-1) and the asymmetric vibration differing by 9 cm(-1).