Department of Physics, Anhui Normal University, Wuhu 241000, People's Republic of China.
J Chem Phys. 2011 Sep 28;135(12):124301. doi: 10.1063/1.3640415.
The first ab initio potential energy surface of the Kr-OCS complex is developed using the coupled-cluster singles and doubles with noniterative inclusion of connected triples [CCSD(T)]. The mixed basis sets, aug-cc-pVTZ for the O, C, and S atom, and aug-cc-pVQZ-PP for the Kr atom, with an additional (3s3p2d1f) set of midbond functions are used. A potential model is represented by an analytical function whose parameters are fitted numerically to the single point energies computed at 228 configurations. The potential has a T-shaped global minimum and a local linear minimum. The global minimum occurs at R = 7.146 a(0), θ = 105.0° with energy of -270.73 cm(-1). Bound state energies up to J = 9 are calculated for three isotopomers (82)Kr-OCS, (84)Kr-OCS, and (86)Kr-OCS. Analysis of the vibrational wavefunctions and energies suggests the complex can exist in two isomeric forms: T-shaped and quasi-linear. The calculated transition frequencies and spectroscopic constants of the three isotopomers are in good agreement with the experimental values.
首次使用包含非迭代连接三的耦合簇单双计算（CCSD(T)）方法开发了 Kr-OCS 配合物的从头势能面。采用混合基组，O、C 和 S 原子采用 aug-cc-pVTZ，Kr 原子采用 aug-cc-pVQZ-PP，外加一个中键函数（3s3p2d1f）集。势能模型由解析函数表示，其参数通过数值拟合到在 228 个构型上计算得出的单点能。该势能具有 T 形全局最小值和局部线性最小值。全局最小值出现在 R = 7.146 a(0)，θ = 105.0°，能量为-270.73 cm(-1)。计算了三种同位素（82）Kr-OCS、（84）Kr-OCS 和（86）Kr-OCS 的三个同位素到 J = 9 的束缚态能。振动波函数和能量的分析表明，配合物可以存在两种异构形式：T 形和准线性。三种同位素的计算跃迁频率和光谱常数与实验值吻合良好。
