School of Physics, Shandong University, Jinan 250100, China.
J Chem Phys. 2011 Dec 21;135(23):234301. doi: 10.1063/1.3668084.
Adiabatic (1A' or 1A'' state) and non-adiabatic (2A'/1A' states) quantum dynamics calculations have been carried out for the title reaction (O((1)D) + D(2) → OD + D) to obtain the initial state-specified (v(i) = 0, j(i) = 0) integral cross section and rate constant using the potential energy surfaces of Dobbyn and Knowles. A total of 50 partial wave contributions have been calculated using the Chebyshev wave packet method with full Coriolis coupling to achieve convergence up to the collision energy of 0.28 eV. The total integral cross section and rate constant are in excellent agreement with experimental as well as quasi-classical trajectory results. Contributions from the adiabatic pathway of the 1A'' state and the non-adiabatic pathway of the 2A'/1A' states, increase significantly with the collision energy. Compared to the O((1)D) + H(2) system, the kinetic isotope effect (k(D)/k(H)) is found to be nearly temperature independent above 100 K and its value of 0.77 ± 0.01 shows excellent agreement with the experimental result of 0.81.
已针对标题反应（O((1)D) + D(2) → OD + D）进行了绝热（1A' 或 1A'' 态）和非绝热（2A'/1A' 态）量子动力学计算，以使用 Dobbyn 和 Knowles 的势能面获得初始态指定（v(i) = 0，j(i) = 0）积分截面和速率常数。使用 Chebyshev 波包方法和完整的科里奥利耦合计算了总共 50 个部分波贡献，以达到碰撞能量为 0.28 eV 的收敛。总积分截面和速率常数与实验以及准经典轨迹结果非常吻合。1A'' 态的绝热途径和 2A'/1A' 态的非绝热途径的贡献随着碰撞能量的增加而显著增加。与 O((1)D) + H(2) 体系相比，在 100 K 以上，动力学同位素效应（k(D)/k(H)）几乎与温度无关，其值 0.77 ± 0.01 与实验结果 0.81 非常吻合。
