Zhou Yanzi, Xie Daiqian
Institute of Theoretical and Computational Chemistry, Laboratory of Mesoscopic Chemistry, Department of Chemistry, Nanjing University, China.
J Chem Phys. 2005 May 1;122(17):174312. doi: 10.1063/1.1888567.
We report two ab initio intermolecular potential energy surfaces for Ne-HCCCN using a supermolecular method. The calculations were performed at the fourth-order Møller-Plesset (MP4) and the coupled cluster singles-and-doubles with noniterative inclusion of connected triples [CCSD(T)] levels with the full counterpoise correction for the basis set superposition error and a large basis set including bond functions. The complex was found to have a planar T-shaped structure minimum and a linear minimum with the Ne atom facing the H atom. The two-dimensional discrete variable representation method was employed to calculate the rovibrational bound states. In addition, the microwave spectra including intensities for the ground vibrational state were predicted. The results show that the spectrum is dominated by b-type (DeltaK(a) = +/-1) transitions with very weak a-type (DeltaK(a) = 0) transitions. The calculated results at the CCSD(T) potential are in good agreement with those at MP4 potential.
我们使用超分子方法报告了Ne-HCCCN的两个从头算分子间势能面。计算在四阶Møller-Plesset（MP4）以及耦合簇单双激发并非迭代包含连接三重激发[CCSD(T)]水平下进行，对基组叠加误差进行了完全的抵消校正，并使用了包含键函数的大基组。发现该复合物具有平面T形结构最小值和线性最小值，其中Ne原子朝向H原子。采用二维离散变量表示法计算振转束缚态。此外，预测了包括基振动态强度在内的微波光谱。结果表明，光谱以b型（ΔK(a) = ±1）跃迁为主，a型（ΔK(a) = 0）跃迁非常弱。在CCSD(T)势能下的计算结果与在MP4势能下的计算结果吻合良好。
