期刊
COMPUTATIONAL AND THEORETICAL CHEMISTRY
卷 1003, 期 -, 页码 71-78出版社
ELSEVIER
DOI: 10.1016/j.comptc.2012.09.009
关键词
Reduced density matrices; Cumulant densities; Chemical bonding; Quantum theory of atoms in molecules
资金
- Spanish MICINN [CTQ2009-08376]
- European Union FEDER funds
- MALTA-Consolider program [CSD2007-00045]
- FICyT [IB09-019]
Real space techniques in the theory of the chemical bond may in fact be understood as means to obtain chemical information from reduced density matrices (RDMs). Much work has been devoted to examine the one particle density, but the renewed interest in electron correlation effects on bonding has progressively shifted research towards further order densities. Up to date, however, not much work has been carried out to determine higher order RDMs from standard electronic structure packages beyond the single-determinant level. We show in this work a possible efficient route to this end. We discuss how to compute RDMs from multi-determinant wavefunctions, how to construct from them nth order cumulant density matrices (n-CDMs), and how to make profit of the recursivity and extensivity of the latter to define a full hierarchy of bonding indices through exhaustive partitions of the physical space. This hierarchy includes a full set of one- to n-center quantities (multi-center bonding indices) which may be conveniently decomposed into one-electron components, each of them partnered with a one-electron function (natural adaptive orbital, NAdO). Illustrative results are obtained and discussed for a set of simple test molecules. (c) 2012 Elsevier B.V. All rights reserved.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据