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. 2012 Jun 7;136(21):214307. doi: 10.1063/1.4725715.
We report a new three-dimensional ab initio intermolecular potential energy surface for the Ne-H(2)S complex with H(2)S monomer fixed at its experimental average structure. Using the supermolecular approach, the intermolecular potential energies were evaluated at CCSD(T) (coupled cluster with single and double and perturbative triple excitations) level with large basis sets including bond functions. The full counterpoise procedure was employed to correct the basis set superposition error. The planar T-shaped global minimum is located at the intermolecular distance of 3.51 Å with a well depth of 71.57 cm(-1). An additional planar local minimum was found to be separated from the global minimum with an energy barrier of 23.11 cm(-1). In addition, two first-order and one second-order saddle points were also located. The combined radial discrete variable representation/angular finite basis representation method and the Lanczos algorithm were employed to evaluate the rovibrational energy levels for eight isotopic species of the Ne-H(2)S complexes. The rotational transition frequencies for the eight isotopomers were also determined for the ground and first vibrational excited states, which are all in very good agreement with the available experimental values.
我们报道了 Ne-H(2)S 复合物的一个新的三维从头算分子间势能面，其中 H(2)S 单体固定在其实验平均结构上。使用超分子方法，在包括键函数的大基组上，在 CCSD(T)（耦合簇与单重和双重以及微扰三重激发）水平上评估了分子间势能。采用完全补偿程序来校正基组叠加误差。平面 T 形全局最小值位于 3.51 Å 的分子间距离处，势阱深度为 71.57 cm(-1)。发现一个额外的平面局部最小值与全局最小值分离，能量势垒为 23.11 cm(-1)。此外，还定位了两个一阶和一个二阶鞍点。采用组合的径向离散变量表示/角有限基表示方法和 Lanczos 算法来评估 Ne-H(2)S 复合物的八个同位素物种的转动振动能级。还确定了八个同位素的基态和第一振动激发态的旋转跃迁频率，这些与可用的实验值非常吻合。
