CAJ | 학술논문

采用内收缩多参考组态相互作用（ icMRCI）方法结合Dunning等相关一致基，计算SiCl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SiCl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。
채용내수축다삼고조태상호작용（ icMRCI）방법결합Dunning등상관일치기，계산SiCl자유기X2Π화A2Σ＋태적세능곡선。토론삼고능화상관능외추대X2Π화A2Σ＋태광보적영향。대세능진행상대론수정급핵개수정계산。의합세능곡선득도X2Π화A2Σ＋태적광보상수。타문여실험결과일치。이용Breit?Pauli산부，계산선궤우합효응，득도X2Π1／2화X2Π3／2적세능곡선、병계산타문적광보상수。구해쌍원자분자핵운동적경향Schr?dinger방정，획득무전동SiCl자유기2개Λ?S태급X2Π태적우합분렬태적전부진동태。득도J＝0시X2Π태적자선?궤도우합상수、교고진동태적관성전동상수이급X2Π1／2화X2Π3／2적진동능급등분자상수。
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 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 X2Π1/2 and X2Π3/2 states are computed. Spectroscopic parameters of twoΩstates are determined. Vibration manifolds are evaluated for twoΛ?S and twoΩstates of non?rotation SiCl 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.