Qu Z-W, Zhu H, Grebenshchikov S Yu, Schinke R
Max-Planck-Institut für Dynamik und Selbstorganisation, D-37073 Göttingen, Germany.
J Chem Phys. 2005 Aug 15;123(7):074305. doi: 10.1063/1.2001650.
Three-dimensional diabatic potential energy surfaces for the lowest four electronic states of ozone with 1A' symmetry-termed X, A, B, and R-are constructed from electronic structure calculations. The diabatization is performed by reassigning corresponding energy points. Although approximate, these diabatic potential energy surfaces allow one to study the uv photodissociation of ozone on a level of theory not possible before. In the present work photoexcitation in the Hartley band and subsequent dissociation into the singlet channel, O3X+hnu-->O(1D)+O2(a 1Deltag), are investigated by means of quantum mechanical and classical trajectory calculations using the diabatic potential energy surface of the B state. The calculated low-resolution absorption spectrum as well as the vibrational and rotational state distributions of O2(a 1Deltag) are in good agreement with available experimental results.
通过电子结构计算构建了具有(1A')对称性（分别称为(X)、(A)、(B)和(R)）的臭氧最低四个电子态的三维非绝热势能面。通过重新分配相应的能量点来进行 diabatic 化。尽管是近似的，但这些 diabatic 势能面使人们能够在以前不可能的理论水平上研究臭氧的紫外光解离。在本工作中，利用(B)态的 diabatic 势能面，通过量子力学和经典轨迹计算研究了哈特利带中的光激发以及随后解离为单重态通道(O_3(X) + h\nu \rightarrow O(^1D) + O_2(a ^1\Delta_g))的过程。计算得到的低分辨率吸收光谱以及(O_2(a ^1\Delta_g))的振动和转动状态分布与现有实验结果吻合良好。
