Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
J Chem Phys. 2013 Sep 21;139(11):114303. doi: 10.1063/1.4820792.
State-to-state photodissociation dynamics of D2O in the B band has been investigated using the recently developed diabatic potential energy surfaces. Quantum dynamical calculations including the electronic X and B states were carried out using a Chebyshev real wave packet method. The nonadiabatic channel via the DOD conical intersection is facile, direct, and fast, which produces rotationally hot and vibrationally cold OD(X) product. On the other hand, the adiabatic channel on the excited state, leading to the OD(Ã) product, is dominated by long-lived resonances, which depend sensitively on the potential energy surface. The calculated absorption spectra, product state distributions, branching ratios, and angular distributions are in reasonably good agreement with the latest experimental results.
采用最新发展的非绝热势能面研究了 B 带中 D2O 的态态光解动力学。利用切比雪夫实波包方法进行了包括电子 X 和 B 态在内的量子动力学计算。通过 DOD 圆锥交叉的非绝热通道是容易的、直接的和快速的，它产生了旋转热和振动冷的 OD(X)产物。另一方面，导致 OD(Ã)产物的激发态的绝热通道由长寿命共振主导，这对势能面非常敏感。计算的吸收光谱、产物态分布、分支比和角分布与最新的实验结果相当吻合。
