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Experimental and numerical studies were performed on the vibrational energy relaxation in shock-heated CO/N2/Ar mixtures. A laser absorption technique was applied to the time-dependent rovibrational temperature time-history measurements. The vibrational relaxation data of reflected-shock-heated CO were summarized at 1720–3230 K. In shock-tube experiments, the rotational temperature of CO quickly reached equilibrium, whereas a relaxation process was found in the time-dependent vibrational temperature. For the mixture with 1.0% CO and 10.0% N2, the vibrational excitation caused a decrease in the macroscopic thermodynamic temperature of the test gas. In the simulations, the state-to-state (StS) approach was employed, where the vibrational energy levels of CO and N2 are treated as pseudo-species. The vibrational state-specific inelastic rate coefficients of N2–Ar collisions were calculated using the mixed quantum–classical method based on a newly developed three-dimensional potential energy surface. The StS predictions agreed well with the measurements, whereas deviations were found between the Schwartz–Slawsky–Herzfeld formula predictions and the measurements. The Millikan–White vibrational relaxation data of the N2–Ar system were found to have the most significant impact on the model predictions via sensitivity analysis. The vibrational relaxation data of the N2–Ar system were then modified according to the experimental data and StS results, providing an indirect way to optimize the vibrational relaxation data of a specific system. Moreover, the vibrational distribution functions of CO and N2 and the effects of the vibration–vibration–translation energy transfer path on the thermal nonequilibrium behaviors were highlighted. [ABSTRACT FROM AUTHOR]

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]

Knowledge of energy exchange rate constants in inelastic collisions is critically required for accurate characterization and simulation of several processes in gaseous environments, including planetary atmospheres, plasma, combustion, etc. Determination of these rate constants requires accurate potential energy surfaces (PESs) that describe in detail the full interaction region space and the use of collision dynamics methods capable of including the most relevant quantum effects. In this work, we produce an extensive collection of vibration-to-vibration (V–V) and vibration-to-translation/rotation (V–T/R) energy transfer rate coefficients for collisions between CO and N 2 molecules using a mixed quantum-classical method and a recently introduced (A. Lombardi, F. Pirani, M. Bartolomei, C. Coletti, and A. Laganà, Frontiers in chemistry, 7, 309 (2019)) analytical PES, critically revised to improve its performance against ab initio and experimental data of different sources. The present database gives a good agreement with available experimental values of V–V rate coefficients and covers an unprecedented number of transitions and a wide range of temperatures. Furthermore, this is the first database of V–T/R rate coefficients for the title collisions. These processes are shown to often be the most probable ones at high temperatures and/or for highly excited molecules, such conditions being relevant in the modeling of hypersonic flows, plasma, and aerospace applications. [ABSTRACT FROM AUTHOR]