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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Jahn-Teller Effect versus Spin-Orbit Coupling in X~2E CH_3S:An ab Initio Study by the Equation-of-Motion Coupled Cluster Method and Multiconfiguration Quasi-Degenerate Second-Order Perturbation Theory
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Jahn-Teller Effect versus Spin-Orbit Coupling in X~2E CH_3S:An ab Initio Study by the Equation-of-Motion Coupled Cluster Method and Multiconfiguration Quasi-Degenerate Second-Order Perturbation Theory

机译：X〜2E CH_3S中的Jahn-Teller效应与自旋轨道耦合：运动方程耦合簇方法和多配置拟简并二阶摄动理论的从头算研究

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摘要

The equation-of-motion coupled cluster method(EOMIP)using a reference Slater determinant based on the CH_3S~--anion ground state with basis sets of triple-and quadruple-zeta quality was applied for numerical optimizations of geometries of stationary points on adiabatic Jahn-Teller surfaces of the X~2E ground state of CH_3S crossing at the C_(3v)symmetry nuclear configuration.Calculations by the multireference configuration interaction method and multiconfiguration quasi-degenerate second-order perturbation(PT2)theory were also performed with use of a complete active space CASSCF reference wave function.The linear and quadratic Jahn-Teller constants were computed for each of three Jahn-Teller active modes.The potential surfaces corresponding to spin-orbit states ~2Ea/2 and ~2E|/2 were obtained with eigenenergies of the full Breit-Pauli spin-orbit operator with a PT2-CASSCF reference wave function.The one-and two-electron scalar relativistic effects were included in CASSCF and spin-orbit calculations.The calculated Jahn-Teller stabilization energy,the barrier to pseudorotation,and the spin-orbit splitting are 93,15,and 358 cM~(-1),respectively.The Jahn-Teller distortions are totally quenched by the strong spin-orbit coupling.The recommended values of the geometry parameters of CH_3S are R_e(CS)= 1.794 A,R_e(CH)= 1.087 A,and alpha_e(HCS)= 109.8°.
机译：将基于CH_3S〜-阴离子基态并具有三重和四重Zeta质量基集的参考Slater行列式的运动方程耦合聚类方法（EOMIP）用于绝热上固定点几何形状的数值优化CH_3S在C_（3v）对称核构型上交叉的X〜2E基态的Jahn-Teller表面。通过多参考构型相互作用方法和多构型拟简并二次扰动（PT2）理论进行了计算完整的有源空间CASSCF参考波函数。针对三个Jahn-Teller有源模式分别计算线性和二次Jahn-Teller常数。获得了与自旋轨道状态〜2Ea / 2和〜2E | / 2对应的势面具有完整的Breit-Pauli自旋轨道算子的本征能和PT2-CASSCF参考波函数.CASSCF和自旋轨道包括一电子和二电子标量相对论效应计算得出的Jahn-Teller稳定能，伪旋转势垒和自旋轨道分裂分别为93、15和358 cM〜（-1）。轨道耦合.CH_3S的几何参数的推荐值为R_e（CS）= 1.794 A，R_e（CH）= 1.087 A，alpha_e（HCS）= 109.8°。

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