分子间相互作用理论研究现状及进展

Status and progress of intermolecular interaction theory

简要介绍了近年来国内外分子间相互作用的理论状况与进展,主要是超分子方法(SM)、对称性匹配微扰理论(SAPT)、密度泛函理论(DFT)、定域相关方法及多种方法的结合对分子间相互作用的研究。在计算与模拟精确势能面(PES)时,超分子方法与微扰方法有效的结合,可以相互补充。SAPT与DFT的结合正在成为分子间作用理论的一种新近趋势。定域相关方法是一种选择性超分子方法,正在向更高水平的Mφller-P lesset微扰理论方向发展。当前对反映分子间主要电子相关效应的色散项的描述和计算仍有一定困难,并有相当挑战性。此外,阐述了分子间作用计算中所出现的基组问题,包括基组叠加误差及其均衡校正方案(counterpoise procedure,CP)存在的争议和基组饱和(basis set saturation)问题。

A review about status and progress of the intermolecular interaction theory is given. Several theoretical methods are discussed , including the supermolecular approach （ SM ） , symmetry-adapted perturbation theory （ SAPT）, density functional theory （DFT） , local-correlation method and the combination of multi-method. The supermolecular and perturbation approaches are in general comple- mentary rather than competitive in calculating and modeling accurate potential PESs （potential energy surfaces, PES）. The local-correlation method has recently emerged as an alternative supermolecular approach for the study of intermolecular interactions and is currently being extended to the higher levels of the Moller-Plesset perturbation theories. There is a difficulty and challenge in calculating dispersion contribution representing the intermolecular main electron correlation effect. In addition, the basis set problems with the calculation of intermolecular interactions are discussed, including basis set superposition error and the argument about counterpoise procedure and basis set saturation.