Effect of the overall rotation on the cis-trans isomerization of HONO induced by an external field

Matthieu Sala (1) , Fabien Gatti (1) , David Lauvergnat (2) , Hans-Dieter Meyer (3)

1 ICGM ICMMM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier
2 LCPO - Laboratoire de Chimie Physique D'Orsay
3 Theoretische Chemie

Rovibrational eigenenergies of HONO are computed and compared to experimental energies available in the literature. For their computation, we use a previously developed potential energy surface (PES) and a newly derived exact kinetic energy operator (KEO) including the overall rotation for a tetra-atomic molecule in non-orthogonal coordinates. In addition, we use the Heidelberg Multi-Configuration Time-Dependent Hartree (MCTDH) package. We compare the experimental rovibrational eigenvalues of HONO available in the literature with those obtained with MCTDH and a previously developed potential energy surface (PES) [F. Richter et al., J. Chem. Phys., 2004, 120, 1306.] for the cis geometry. The effect of the overall rotation on the process studied in our previous work on HONO [F. Richter et al., J. Chem. Phys., 2007, 127, 164315.] leading to the cis - trans isomerization of HONO is investigated. This effect on this process is found to be weak.

Domaines: Chimie théorique et/ou physique

Matthieu Sala, Fabien Gatti, David Lauvergnat, Hans-Dieter Meyer. Effect of the overall rotation on the cis-trans isomerization of HONO induced by an external field. Physical Chemistry Chemical Physics, 2012, 14, pp.3791. ⟨10.1039/c2cp23709a⟩. ⟨hal-00672953⟩