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优化有效势方法:对于有限轨道基组,是否有可能获得响应函数的精确表示?

Optimized effective potential method: is it possible to obtain an accurate representation of the response function for finite orbital basis sets?

作者信息

Kollmar Christian, Filatov Michael

机构信息

Department of Theoretical Chemistry, Zernike Institute for Advanced Materials, Rijksuniversiteit Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.

出版信息

J Chem Phys. 2007 Sep 21;127(11):114104. doi: 10.1063/1.2777144.

Abstract

The optimized effective potential (OEP) equations are solved in a matrix representation using the orbital products of occupied and virtual orbitals for the representation of both the local potential and the response function. This results in a direct relationship between the matrix elements of local and nonlocal operators for the exchange-correlation potential. The effect of the truncation of the number of such products in the case of finite orbital basis sets on the OEP orbital and total energies and on the spectrum of eigenvalues of the response function is examined. Test calculations for Ar and Ne show that rather large AO basis sets are needed to obtain an accurate representation of the response function.

摘要

利用占据轨道和虚拟轨道的轨道积来表示局域势和响应函数,在矩阵表示中求解优化有效势(OEP)方程。这导致了交换相关势的局域算符和非局域算符的矩阵元之间的直接关系。研究了在有限轨道基组情况下此类积的数量截断对OEP轨道和总能量以及响应函数本征值谱的影响。对氩和氖的测试计算表明,需要相当大的原子轨道基组才能准确表示响应函数。

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