期刊
JOURNAL OF CHEMICAL PHYSICS
卷 129, 期 18, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.3007987
关键词
density functional theory; electron correlations; HF calculations; hydrogen neutral molecules; localised states; molecular electronic states; potential energy surfaces; van der Waals forces
资金
- Comunidad Autonoma de Madrid (CAM) [S-0505/MAT/0303]
- Ministerio de Ciencia e Innovacion [CTQ2007-62898, FIS2007-62006, CTQ2007-63332, MAT2007-60966]
A new embedding method to include local correlation in large systems is proposed. In this method the density of the whole system, calculated via density functional theory approaches, is partitioned in two pieces, one corresponding to the subsystem of interest and the rest to the environment. In the second step, an embedding potential is obtained iteratively using as a driving force the self-repulsion due to the density difference, in a similar form as proposed by Zhao [Phys. Rev. A 50, 2138 (1994)], to obtain the exact exchange-correlation functional. Such potential is added to the Fock equation to build the localized molecular orbitals which are further used to include the local electronic correlation in the subsystem of interest. This method is an alternative to the previous DFT-based embedding methods first proposed by Wesolowski and Washell [J. Phys. Chem. 97, 8050 (1993)] and after enhanced by Govind [J. Chem. Phys. 110, 7677 (1999)] and adapted to metal extended systems, which use density functionals to describe the kinetic energy contribution to the embedding potential, whose precise form has been largely treated in the literature and its crucial role is discussed here. The method is applied to hydrogen chains and its van der Waals interaction with H-2. The results obtained are in very good agreement with exact calculations performed on the whole system, which demonstrates that the method proposed is a very promising route to introduce correlation in large systems.
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