Issue 28, 2019

Explicitly correlated potential energy surface of the CO2–CO van der Waals dimer and applications

Abstract

The four-dimensional-potential energy surface (4D-PES) of the CO2–CO van der Waals complex is generated using the explicitly correlated coupled cluster with single, double, and perturbative triple excitation (CCSD(T)-F12) method in conjunction with the augmented correlation-consistent triple zeta (aug-cc-pVTZ) basis set. This 4D-PES is developed over the set of inter-molecular coordinates and where the CO2 and CO monomers are treated as rigid rotors. Afterwards, analytic fits of this 4D-PES are carried out. In addition to the already known C-bound and O-bound stable structures of CO2–CO, we characterise a new isomer: it has a T-shaped structure where the O atom of the CO2 moiety points into the centre of mass of CO. We also find the saddle points connecting these minimal structures. This new isomer may play a role during the intramolecular isomerization processes at low energies. Then, the 4D-PES expansion is incorporated into bound vibrational state computations of C-bound and O-bound complexes. We also computed the temperature dependence of the second virial coefficient for CO2–CO. A good agreement with experiments is found.

Graphical abstract: Explicitly correlated potential energy surface of the CO2–CO van der Waals dimer and applications

Supplementary files

Article information

Article type
Paper
Submitted
10 May 2019
Accepted
26 Jun 2019
First published
28 Jun 2019

Phys. Chem. Chem. Phys., 2019,21, 15871-15878

Explicitly correlated potential energy surface of the CO2–CO van der Waals dimer and applications

A. Badri, L. Shirkov, N. Jaidane and M. Hochlaf, Phys. Chem. Chem. Phys., 2019, 21, 15871 DOI: 10.1039/C9CP02657F

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