Effective Hamiltonians for the Fermi resonance – Interacting states of C3vC3v molecules

Kamil Sarka (1) , Lucie Nová Stříteská (1, 2) , Adina Ceausu-Velcescu (3)

1 Comenius University in Bratislava
2 Department of Analytical Chemistry
3 LAMPS - LAboratoire de Modélisation Pluridisciplinaire et Simulations

A global reduction theory of the vibration–rotational Hamiltonian of C3v closed-shell molecules, dealing with all possible anharmonic interactions in which a fundamental vibration can be involved, is presented. The effective correlation-free Hamiltonians and the corresponding matrix elements are derived. The cases studied here are (i) a fundamental band interacting with an overtone, (ii) a fundamental band interacting with a combination band. The Hamiltonian terms H30;H31;H32 and the recommended set of parameters following from the appropriate reductions are presented. The results are provided in a form directly applicable to the analysis of spectra of the interacting states.

Mots clés: Vibrational–rotational Hamiltonian; Contact transformation; Hamiltonian reduction; C3vC3v molecules; Fermi resonance; Anharmonic resonance; Matrix element

Domaines: Physique [physics]

Kamil Sarka, Lucie Nová Stříteská, Adina Ceausu-Velcescu. Effective Hamiltonians for the Fermi resonance – Interacting states of C3vC3v molecules. Journal of Molecular Spectroscopy, 2014, http://linkinghub.elsevier.com/retrieve/pii/S0022285214001842. ⟨10.1016/j.jms.2014.09.003⟩. ⟨hal-01143140⟩