The mode specificity plays an important role in understanding the fundamental reaction dynamics. This work reports a theoretical study of the rotational mode specificity of the reactant CHD3(JK) in the prototypical hy...The mode specificity plays an important role in understanding the fundamental reaction dynamics. This work reports a theoretical study of the rotational mode specificity of the reactant CHD3(JK) in the prototypical hydrocarbon oxidation reaction O(3P)+CHD3→OH+CD3. The time-dependent quantum wave packet method combined with a seven-dimensional reduced model is employed to calculate the reaction probability on an accurate potential energy surface. The obtained reaction probability depends on the values of both K and Ktot with PKtot=K=0>PKtot=K=J>PKtot=J,K=0=PKtot=0,K=J. This observation can be well rationalized by the reactant alignment pictures. Rotational excitations of CHD3 up to the angular momentum quantum number J=4 have a very weak enhancement effect on the reaction except for the state (J=4, K=0). In addition, the rotationally excited states of CHD3 with K=0 promote the reaction more than those with K=J. The quantum dynamics calculations indicate that the K=0 enhancements are mainly caused by the contributions from the components with K=Ktot=0. The components correspond to the tumbling rotation of CHD3, which enlarges the range of the reactive initial attack angles.展开更多
基金supported by the National Natural Science Foundation of China (No.21773297 to Ming-hui Yang, No.21703210 to Rui Liu, and No.21603266 to Hong-wei Song)China Postdoctoral Science Foundation funded Project under Grant 2017M610492
文摘The mode specificity plays an important role in understanding the fundamental reaction dynamics. This work reports a theoretical study of the rotational mode specificity of the reactant CHD3(JK) in the prototypical hydrocarbon oxidation reaction O(3P)+CHD3→OH+CD3. The time-dependent quantum wave packet method combined with a seven-dimensional reduced model is employed to calculate the reaction probability on an accurate potential energy surface. The obtained reaction probability depends on the values of both K and Ktot with PKtot=K=0>PKtot=K=J>PKtot=J,K=0=PKtot=0,K=J. This observation can be well rationalized by the reactant alignment pictures. Rotational excitations of CHD3 up to the angular momentum quantum number J=4 have a very weak enhancement effect on the reaction except for the state (J=4, K=0). In addition, the rotationally excited states of CHD3 with K=0 promote the reaction more than those with K=J. The quantum dynamics calculations indicate that the K=0 enhancements are mainly caused by the contributions from the components with K=Ktot=0. The components correspond to the tumbling rotation of CHD3, which enlarges the range of the reactive initial attack angles.
