SiCl自由基X^2Π和A^2Σ^+态的光谱性质  

Spectroscopic Properties of SiCl( X^2Π,A^2Σ^+) Radical

作　　者：刘慧[1] 邢伟[1] 施德恒[2] 孙金锋[2] 朱遵略[2] 

机构地区：[1]信阳师范学院物理电子工程学院,信阳464000 [2]河南师范大学物理与电子工程学院,新乡453007

出　　处：《计算物理》2015年第5期610-616,共7页Chinese Journal of Computational Physics

基　　金：国家自然科学基金(61077073);河南省科技计划项目(142300410201);河南省教育厅科技计划重点项目(14B140023)资助项目

摘　　要：采用内收缩多参考组态相互作用(ic MRCI)方法结合Dunning等相关一致基,计算Si Cl自由基X2Π和A2Σ+态的势能曲线.讨论参考能和相关能外推对X2Π和A2Σ+态光谱的影响.对势能进行相对论修正及核价修正计算.拟合势能曲线得到X2Π和A2Σ+态的光谱常数.它们与实验结果一致.利用Breit-Pauli算符,计算旋轨耦合效应,得到X2Π1/2和X2Π3/2的势能曲线、并计算它们的光谱常数.求解双原子分子核运动的径向Schrdinger方程,获得无转动Si Cl自由基2个Λ-S态及X2Π态的耦合分裂态的全部振动态.得到J=0时X2Π态的自旋-轨道耦合常数、较高振动态的惯性转动常数以及X2Π1/2和X2Π3/2的振动能级等分子常数.Potential energy curves （PEC） of ground X2Π and A2Σ＋ states of SiCl radical are calculated with internally contracted multireference configuration interaction approach in combination with Dunning’ s correlationconsistent basis sets. Reference energy and correlation energy are extrapolated to complete basis set limit. Scalar relativistic and corevalence correlation corrections are calculated. Spectroscopic parameters of X2Π and A2Σ＋ states are obtained. With BreitPauli operator, PECs of X2Π1/2 and X2Π3/2 states are computed. Spectroscopic parameters of twoΩstates are determined. Vibration manifolds are evaluated for twoΛS and twoΩstates of nonrotation SiCl radical by numerically solving radical Schrdinger equation of nuclear motion. For each vibrational state, vibrational levels and inertial rotation constants, spinorbital coupling constants of X2Π state are determined.

关 键 词：势能曲线 光谱常数 能量外推 自旋-轨道耦合 

分 类 号：O561.3[理学—原子与分子物理]