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

Literature Information

Publication Date 2019-06-28
DOI 10.1039/C9CP02657F
Impact Factor 3.676
Authors

Leonid Shirkov, Nejm-Eddine Jaidane, Majdi Hochlaf


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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.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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