The theoretical prediction of infrared spectra of trans- and cis-hydroxycarbene calculated using full dimensional ab initio potential energy and dipole moment surfaces

Lucas Koziol; Yimin Wang; Bastiaan J Braams; Joel M Bowman; Anna I Krylov

doi:10.1063/1.2925452

The theoretical prediction of infrared spectra of trans- and cis-hydroxycarbene calculated using full dimensional ab initio potential energy and dipole moment surfaces

J Chem Phys. 2008 May 28;128(20):204310. doi: 10.1063/1.2925452.

Authors

Lucas Koziol¹, Yimin Wang, Bastiaan J Braams, Joel M Bowman, Anna I Krylov

Affiliation

¹ Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482, USA.

PMID: 18513022
DOI: 10.1063/1.2925452

Abstract

Accurate infrared spectra of the two hydroxycarbene isomers are computed by diagonalizing the Watson Hamiltonian including up to four mode couplings using full dimensional potential energy and dipole moment surfaces calculated at the CCSD(T)/cc-pVTZ (frozen core) and CCSD6-311G(**) (all electrons correlated) levels, respectively. Anharmonic corrections are found to be very important for these elusive higher-energy isomers of formaldehyde. Both the energy levels and intensities of stretching fundamentals and all overtone transitions are strongly affected by anharmonic couplings between the modes. The results for trans-HCOHHCOD are in excellent agreement with the recently reported IR spectra, which validates our predictions for the cis-isomers.