求解弱相互作用分子A-BC的振转能级和波函数的SCF-CI方法

给出了一种计A－BC型弱相互作用分子体系的分子间振转激发态的自洽场-组态相互作用(SCF－CI)方法. 首先使用SCF方法代化径向伸缩振动和弯曲振动的基函数,再用CI方法确定精确的振转激发态能级. 在求解-维的伸缩振动SCF方程时,采用Numerov－Johnson算法在给定区间上求解获得振动波函数的数值解. 具体计算了Ar－HCI和Ar－N₂体系的振转激发态的能级以验证该方法. 结果表明,本方法可用较少的组态就能获得可与其它大计算量的方法具有相比拟的精度的结果.

A Vibrational SCF-CI Method for Determining Rovibrational Eigenstates of Weakly Bound Complexes

A vibrational self-consistent field-configuration-interaction(SCF-CI)method for determining rovibrational eigenstates of weakly bound A-BC complexes is suggested.In theSCF-CI method, the SCF method is used to optimize the basis sets for intermolecular bend-ing and stretching motions, then the CI method is used to determine the precise rovibrationalenergy levels and the wavefunctions. The radial basis function is not an analytical form, butis determined numerically from the stretching one dimensional SCF equation by using therenormalized Numerov-Johnson algorithm. The related integrals over the radial basis func-tions can be evaluated conveniently by using the HEG quadrature. In order to test this SCF-CI method, the calculated results of the rovibrational bound states for Ar-HCl and Ar-N2complexes are presented together with comparison of the results obtained from other theoret-ical approaches- The results show that the SCF-CI method may provide a comparable level ofaccuracy by using fewer configurations-