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He-H2S复合物的六维从头算势能面和束缚态
韩超英1, 蒋 婷1, 朱 华*1, 范红筠*2
1.四川大学化学学院,成都 610064;2.四川轻化工大学生物工程学院,自贡 643000
摘要:
采用[CCSD(T)]-F12a/aug-cc-pVTZ方法,同时在基组中引入中心键函数(3s3p2d1f1g)构建了He-H$_2$S复合物的高精度六维势能面. 除分子间振动坐标,同时考虑了H2S分子内的v1对称伸缩振动Q1正则模、v2弯曲振动Q2正则模和v3反对称伸缩振动Q3正则模三种振动模式. 将计算得到的六维势能面在Q1Q2Q3方向上分别做积分得到H2S单体分别处于振动基态、vv3激发态下的He-H2S的三个振动平均势能面. 计算结果表明,每个平均势能面都有一个T形全局极小值、一个平面局部极小值、两个平面内鞍点和一个平面外鞍点. 全局极小值的几何构型位于R=3.46 ?,θ=109.9°和φ=0.0°,势阱深度为35.301 -1. 在径向部分采用离散变量表象法和角度部分采用有限基组表象法并结合Lanczos循环算法计算了He-H2S的振转能级和束缚态. 计算发现He-(para-H2S)在H2S的v2v3区域的带心位移分别为0.025 cm-1和0.031 cm-1,而He-(ortho-H2S)的带心位移分别为0.041 cm-1和0.060 cm-1,都表现为蓝移.
关键词:  He-H2S,势能面,束缚态
DOI:10.1063/1674-0068/cjcp1907145
分类号:
基金项目:
Six-Dimensional ab initio Potential Energy Surface and Bound States for He-H2S Complex
Chao-ying Han1, Ting Jiang1, Hua Zhu*1, Hong-jun Fan*2
1.School of Chemistry, Sichuan University, Chengdu 610064, China;2.School of Biological Engineering, Sichuan University of Science & Engineering, Zigong 643000, China
Abstract:
We present a new six-dimensional potential energy surface for He-H2S including the in-tramolecular Q1, Q2, and Q3 normal modes for the v1 symmetric stretching, v2 bending and v3 asymmetric stretching of H2S. The potential was calculated at the coupled-cluster singles and doubles with noniterative inclusion of connected triples [CCSD(T)]-F12a level with augmented correlation-consistent polarized-valence triple-zeta (aug-cc-pVTZ) basis set plus the midpoint bond function (3s3p2d1f1g). Three vibrationally averaged potentials with H2S at the vibrational ground state v1 as well as the excited states v2 and v3 were generated from the integration of the six-dimensional potential over the Q1, Q2 and Q3 coordinates. Each potential has a planar T-shaped global minimum, a planar local minimum, two in-plane saddle points as well as an out-plane saddle point. The global minimum is located at R=3.46 ?, θ=109.9° and φ=0.0° with a well depth of 35.301 cm-1. The radial discrete vari-able representation/angular finite basis representation method and the Lanczos algorithm were employed to calculate the rovibrational energy levels. The calculated band origins areblue-shifted (0.025 cm-1 and 0.031 cm-1) and (0.041 cm-1 and 0.060 cm-1) for He-(para-H2S) and He-(ortho-H2S) in the v2 and v3 region of the H2S molecule, respectively.
Key words:  He-H2S, Potential energy surface, Bound state
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