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Quantum-classical rate coefficient datasets of vibrational energy transfer in carbon monoxide based on highly accurate potential energy surface.
- Source :
- Journal of Chemical Physics; 2/28/2024, Vol. 160 Issue 8, p1-15, 15p
- Publication Year :
- 2024
-
Abstract
- A merged potential energy surface (PES) is introduced for CO + CO collisions by combining a recent full-dimensional ab initio PES [Chen et al. J. Chem. Phys. 153, 054310 (2020)] and analytical long-range multipolar interactions. This merged PES offers a double advantage: it retains the precision of the ab initio PES in describing the van der Waals well and repulsive short range while providing an accurate physical description of long-range interaction; it significantly reduces the computational time required for trajectory integration since the long-range portion of the ab initio PES (involving numerous neural network fitting parameters) is now replaced by the analytical model potential. Based on the present merged PES, mixed Quantum-Classical (MQC) calculations, which capture quantum effects related to vibrational motion, align with a range of experimental data, including transport properties, vibrational energy transfer between CO and its isotoplogues, as well as rate coefficients for V–V and V–T/R processes. Notably, the original ab initio PES yields V–T/R rate coefficients at low temperatures that are significantly higher than the experimental data due to the artificial contribution of its unphysical long-range potential. In addition to conducting extensive MQC calculations to obtain raw data for V–V and V–T/R rate coefficients, we employ Gaussian process regression to predict processes lacking computed MQC data, thereby completing the considered V–V and V–T/R datasets. These extensive rate coefficient datasets, particularly for V–T/R processes, are unprecedented and reveal the significant role played by V–T/R processes at high temperatures, emphasizing the necessity of incorporating both V–V and V–T/R processes in the applications. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00219606
- Volume :
- 160
- Issue :
- 8
- Database :
- Complementary Index
- Journal :
- Journal of Chemical Physics
- Publication Type :
- Academic Journal
- Accession number :
- 175757129
- Full Text :
- https://doi.org/10.1063/5.0189772