N(D) + H(X∑)散射反应三个最低电子态的精确势能面
Accurate Potential Energy Surfaces for the Three Lowest Electronic States of N(D) + H(X∑ ) Scattering Reaction.
作者信息
Wang Dequan, Shi Guang, Fu Liwei, Yin Ruilin, Ji Youbo
机构信息
Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China.
Hematology and Oncology Department and Pain Department, The Second Hospital, Jilin University, Changchun 130041, People's Republic of China.
出版信息
ACS Omega. 2019 Jul 15;4(7):12167-12174. doi: 10.1021/acsomega.9b01395. eCollection 2019 Jul 31.
The three lowest full three-dimensional adiabatic and three diabatic global potential energy surfaces are reported for the title system. The accurate ab initio method (MCSCF/MRCI) with larger basis sets (aug-cc-pVQZ) is used to reduce the adiabatic potential energies, and the global adiabatic potential energy surfaces are deduced by a three-dimensional B-spline fitting method. The conical intersections and the mixing angles between the lowest three adiabatic potential energy surfaces are precisely studied. The most possible nonadiabatic reaction pathways are predicted, i.e., N(D) + H(X∑ ) → NH(2A') → CI (1A'-2A') → NH(1A') → CI (1A″-1A') → NH(1A″) → NH(X∑) + H(S). The products of the first excited state (NH(aΔ) + H(S)) and the second excited state (NH(b∑ ) + H(S)) can be generated in these nonadiabatic reaction pathways too.
报道了该标题体系的三个最低的全三维绝热和三个非绝热全局势能面。采用具有更大基组（aug-cc-pVQZ）的精确从头算方法（MCSCF/MRCI）来降低绝热势能，并通过三维B样条拟合方法推导全局绝热势能面。精确研究了最低的三个绝热势能面之间的锥形交叉点和混合角。预测了最可能的非绝热反应途径，即N(D)+H(X∑)→NH(2A')→CI(1A'-2A')→NH(1A')→CI(1A″-1A')→NH(1A″)→NH(X∑)+H(S)。在这些非绝热反应途径中也可以产生第一激发态（NH(aΔ)+H(S)）和第二激发态（NH(b∑)+H(S)）的产物。
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