Vibrational treatment of the formic acid double minimum case in valence coordinates.

Falk Richter (1) , Philippe Carbonnière (1)

1 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux

One single full dimensional valence coordinate HCOOH ground state potential energy surface accurate for both cis and trans conformers for all levels up to 6000 cm-1 relative to trans zero point energy has been generated at CCSD(T)-F12a/aug-cc-pVTZ level. The fundamentals and a set of eigenfunctions complete up to about 3120 and 2660 cm-1 for trans- and cis-HCOOH, resp., have been calcd. and assigned using the improved relaxation method of the Heidelberg multi-configuration time-dependent Hartree package and an exact expression for the kinetic energy in valence coordinates generated by the TANA program. The calcd. trans fundamental transition frequencies agree with expt. to within 5 cm-1. A few reassignments are suggested. Our results discard any cis trans delocalization effects for vibrational eigenfunctions up to 3640 cm-1 relative to trans zero point energy.

Domaines: Chimie

Falk Richter, Philippe Carbonnière. Vibrational treatment of the formic acid double minimum case in valence coordinates.. Journal of Chemical Physics, 2018, 148, pp.6. ⟨10.1063/1.5005989⟩. ⟨hal-01710610⟩