Article Dans Une Revue The Journal of Chemical Physics Année : 2014

A new accurate ground-state potential energy surface of ethylene and predictions for rotational and vibrational energy levels.

Résumé

In this paper we report a new ground state potential energy surface for ethylene (ethene) C2H4 obtained from extended ab initio calculations. The coupled-cluster approach with the perturbative inclusion of the connected triple excitations CCSD(T) and correlation consistent polarized valence basis set cc-pVQZ was employed for computations of electronic ground state energies. The fit of the surface included 82 542 nuclear configurations using sixth order expansion in curvilinear symmetry-adapted coordinates involving 2236 parameters. A good convergence for variationally-computed vibrational levels of the C2H4 molecule was obtained with a RMS(Obs. − Calc.) deviation of 2.7 cm −1 for fundamental bands centers and 5.9 cm −1 for vibrational bands up to 7800 cm −1. Large scale vibrational and rotational calculations for 12C2H4 , 13C2H4 and 12C2D4 isotopologues were performed using this new surface. Energy levels for J = 20 up to 6000 cm −1 are in a good agreement with observations. This represents a considerable improvement with respect to available global predictions of vibrational levels of 13C2H4 and 12C2D4 and rovibrational levels of 12C2H4 .

Fichier principal
Vignette du fichier
C2H4_PES_bbl.pdf (1.74 Mo) Télécharger le fichier
Appendices.zip (123.75 Ko) Télécharger le fichier
Origine Fichiers produits par l'(les) auteur(s)
Licence
Origine Fichiers produits par l'(les) auteur(s)
Licence
Loading...

Dates et versions

hal-01214173 , version 1 (12-10-2015)

Licence

Identifiants

Citer

Thibault Delahaye, Andrei Nikitin, Michaël Rey, Peter G. Szalay, Vladimir G. Tyuterev. A new accurate ground-state potential energy surface of ethylene and predictions for rotational and vibrational energy levels.. The Journal of Chemical Physics, 2014, 141, pp.104301. ⟨10.1063/1.4894419⟩. ⟨hal-01214173⟩
183 Consultations
736 Téléchargements

Altmetric

Partager

  • More