【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.更多还原

【Abstract】 Potential energy curves( PEC) of ground X2Π and A2Σ+states of Si Cl radical are calculated with internally contracted multireference configuration interaction approach in combination with Dunning’s correlation-consistent basis sets. Reference energy and correlation energy are extrapolated to complete basis set limit. Scalar relativistic and core-valence correlation corrections are calculated.Spectroscopic parameters of X2Π and A2Σ+states are obtained. With Breit-Pauli operator,PECs of X2Π1 /2and X2Π3 /2states are computed. Spectroscopic parameters of two Ω states are determined. Vibration manifolds are evaluated for two Λ-S and two Ω states of non-rotation Si Cl radical by numerically solving radical Schrdinger equation of nuclear motion. For each vibrational state,vibrational levels and inertial rotation constants,spin-orbital coupling constants of X2Π state are determined.更多还原