HD分子X^1∑_g^+,B^1∑_u^+和C^1Ⅱ_u态的势能函数  

Analytical potential energy functions for the electronic states X^1∑_g^+,B^1∑_u^+and C^1П_u of molecule HD

作　　者：尹凯 黄传连[1] 周玲玲[1] 伍冬兰[1] 谢安东[1] 

机构地区：[1]井冈山大学

出　　处：《四川大学学报（自然科学版）》2009年第6期1737-1742,共6页Journal of Sichuan University(Natural Science Edition)

基　　金：国家自然科学基金(10965002)

摘　　要：使用SAC/SAC-CI方法,利用D95++* *、6-311++g* *以及cc-PVTZ等基组,对HD分子的基态(X^1∑_g^+)、第二激发态(B^1∑_u^+)和第三激发态(C^1Ⅱ_u)的平衡结构和谐振频率进行了优化计算.通过对3个基组的计算结果的比较,得出了cc-PVTZ基组为三个基组中的最优基组的结论;使用cc-PVTZ基组,利用SAC的GSUM(Group Sum of Operators)方法对基态(X^1∑_g^+)、SAC-CI的GSUM方法对激发态(B^1∑_u^+)和(C^1Ⅱ_u)进行单点能扫描计算,用正规方程组拟合Murrell-Sorbie函数,得到了相应电子态的完整势能函数;从得到的势能函数计算了与基态(X^1∑_g^+)、第二激发态(B^1∑_u^+)和第三激发态(C^1Ⅱ_u)相对应的光谱常数(B_e,α_e,ω_e和ω_eχ_e),结果与实验数据基本吻合.The energies,equilibrium geometries and harmonic frequencies of the three electronic states (the ground state X^1∑_g^+ ,the second excited state B^1∑_u^+ and the third excited state C^1Π_u) of HD molecule have been calculated using the GSUM (Group Sum of Operators) method of SAC/ SAC-CI with the basis sets D95 ++**,6-311++g** and cc-PVTZ.Comparing among the above-mentioned three basis sets,the conclusion is gained that the basis set cc-PVTZ is the most suitable for the energy calculation of HD molecule.The whole potential curves for these three electronic states are further scanned using SAC/cc-PVTZ method for the ground state and SAC-CI/cc-PVTZ methods for the excited states, then have a least square fitted to Murrell-Sorbie function,and last the spectroscopy constants (B_e,α_e, ω_e,and ω_eχ_e) are calculated,which are in good agreement with the experimental data.It is believed that Murrell-Sorbie function form and SAC/SAC-CI method are suitable not only for the ground state,but the low-lying excited states as well.

关 键 词：分子 势能函数 ground state 三激发态 SAC excited states 基组 basis sets MURRELL-SORBIE函数 energy calculation 优化计算 function three 基态 方法 least square methods for 正规方程组 AGREEMENT 谐振频率 

分 类 号：N55[自然科学总论]