期刊
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
卷 9, 期 9, 页码 3933-3938出版社
AMER CHEMICAL SOC
DOI: 10.1021/ct400547n
关键词
-
资金
- U.S. National Science Foundation [CHE 0844999, 1265945]
- Department of Energy [DE-SC0006863]
- Alfred P. Sloan Foundation
- Gaussian, Inc.
- University of Washington Student Technology Fund
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1265945] Funding Source: National Science Foundation
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0844999] Funding Source: National Science Foundation
A guided self-consistent field (SCF) method is presented in this paper. This method uses the eigenspace update-and-following idea to improve the SCF method for optimizing wave functions that are higher-energy solutions to the Roothaan-Hall equation. In this method, the eigenvectors of the previous SCF step are used to prediagonalize the current Fock/Kohn-Sham matrix, preserving the ordering of orbital occupations. When the subject of interest is an excited state of the same spin symmetry as the ground state, the initial guess of excited wave function is improved with a preconditioning step. The preconditioning step is an SCF iteration applied to the beta spin manifold if the initial guess is generated by orbital permutation in the a spin manifold. This simple preconditioning step gives rise to more-stable SCF convergence using the algorithm presented herein. The guided SCF method is used to optimize ligand-field excited states in tetrahedral transition-metal complexes, and calculate Delta SCF excitation energies. The calculated ligand-field transition energies are compared with those obtained from orbital energy differences, linear response time-dependent density functional theory, and experiments. The excitation energies obtained using the method presented in this work show a significant improvement over orbital energy differences and linear response method.
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