University Chemical Laboratory, Lensfield Road, Cambridge CB2 1EW, U.K., and University College London, 20 Gordon Street, London WC1H 0AJ, U.K.
J Chem Theory Comput. 2008 Jan;4(1):7-18. doi: 10.1021/ct700104t.
The induction energy often plays a very important role in determining the structure and properties of clusters of organic molecules, but only in recent years has an effort been made to include this energy in such calculations, notably in the field of organic crystal structure prediction. In this paper and the following one in this issue we provide ab initio methods suitable for the accurate inclusion of the induction energy for molecules containing as many as 30 atoms or so. These techniques are based on Symmetry-Adapted Perturbation Theory using Density Functional Theory [SAPT(DFT)] and use distributed polarizabilities computed using the recently developed density-fitting algorithm with constrained refinement. With this approach we are able to obtain induction models of varying complexity and study the effects of overlap and related numerical issues. Basis set effects on the exact and asymptotic induction energies are investigated, and the roles of higher-order induction energies and many-body effects are explored.
在确定有机分子团簇的结构和性质时，诱导能常常起着非常重要的作用，但直到近年来，人们才努力在这类计算中纳入这一能量，特别是在有机晶体结构预测领域。在本文和本期的后续文章中，我们提供了适合于准确纳入包含多达 30 个原子左右的分子的诱导能的从头计算方法。这些技术基于使用密度泛函理论的对称性自适应微扰理论（SAPT(DFT)），并使用最近开发的带有约束细化的密度拟合算法来计算分布式极化率。通过这种方法，我们能够获得不同复杂程度的诱导模型，并研究重叠和相关数值问题的影响。我们研究了基组对精确和渐近诱导能的影响，以及高阶诱导能和多体效应的作用。
