Vibrational energy pooling via collisions between asymmetric stretching excited CO2: a quasi-classical trajectory study on an accurate full-dimensional potential energy surface

Dandan Lu; Jun Chen; Hua Guo; Jun Li

doi:10.1039/D1CP03687D

Vibrational energy pooling via collisions between asymmetric stretching excited CO₂: a quasi-classical trajectory study on an accurate full-dimensional potential energy surface†

Dandan Lu,

^ab Jun Chen,^c Hua Guo

^b and Jun Li

*^a

Author affiliations

* Corresponding authors

^a School of Chemistry and Chemical Engineering & Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing 401331, China
E-mail: jli15@cqu.edu.cn

^b Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico, USA

^c State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China

Abstract

In low temperature plasmas, energy transfer between asymmetric stretching excited CO₂ molecules can be highly efficient, which leads to further excitation (and de-excitation) of the CO₂ molecules: CO₂(v_as) + CO₂(v_as) → CO₂(v_as + 1) + CO₂(v_as − 1). Through such a vibrational ladder climbing mechanism, CO₂ can be activated and eventually dissociates. To gain mechanistic insight of such processes, a full-dimensional accurate potential energy surface (PES) for the CO₂ + CO₂ system is developed using the permutational invariant polynomial-neural network method based on CCSD(T)-F12a/AVTZ energies at about 39 000 geometries. This PES is used in quasi-classical trajectory (QCT) studies of the vibrational energy transfer between CO₂ molecules excited in the asymmetric stretching mode. A machine learning algorithm is used to determine state-specific rate coefficients for the vibrational transfer processes from a limited data set. In addition to the CO₂(v_as + 1) + CO₂(v_as − 1) channel, the QCT simulations revealed significant contributions from the CO₂(v_as + 2,3) + CO₂(v_as − 2,3) channels, particularly at low collision energies/temperatures. These multi-vibrational-quantum processes are attributed to enhanced energy flow in the collisional complex formed by enhanced dipole–dipole interaction between asymmetric stretching excited CO₂ molecules.

This article is part of the themed collection: 2021 PCCP HOT Articles

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Article information

DOI: https://doi.org/10.1039/D1CP03687D
Article type: Paper
Submitted: 11 Aug 2021
Accepted: 13 Oct 2021
First published: 14 Oct 2021

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Phys. Chem. Chem. Phys., 2021,23, 24165-24174

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Vibrational energy pooling via collisions between asymmetric stretching excited CO₂: a quasi-classical trajectory study on an accurate full-dimensional potential energy surface

D. Lu, J. Chen, H. Guo and J. Li, Phys. Chem. Chem. Phys., 2021, 23, 24165 DOI: 10.1039/D1CP03687D

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