Computational study of the ro-vibrational spectrum of CO-CO2.
J Chem Phys
; 151(8): 084307, 2019 Aug 28.
Article
em En
| MEDLINE
| ID: mdl-31470713
ABSTRACT
An accurate ab initio ground-state intermolecular potential energy surface (PES) was determined for the CO-CO2 van der Waals dimer. The Lanczos algorithm was used to compute rovibrational energies on this PES. For both the C-in and O-in T-shaped isomers, the fundamental transition frequencies agree well with previous experimental results. We confirm that the in-plane states previously observed are geared states. In addition, we have computed and assigned many other vibrational states. The rotational constants we determine from J = 1 energy levels agree well with their experimental counterparts. Planar and out-of-plane cuts of some of the wavefunctions we compute are quite different, indicating strong coupling between the bend and torsional modes. Because the stable isomers are T-shaped, vibration along the out-of-plane coordinates is very floppy. In CO-CO2, when the molecule is out-of-plane, interconversion of the isomers is possible, but the barrier height is higher than the in-plane geared barrier height.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
J Chem Phys
Ano de publicação:
2019
Tipo de documento:
Article
País de afiliação:
Canadá