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Possibilities for a density matrix theory

机译:密度矩阵理论的可能性

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Two possible routes are considered to arrive at a one-particle reduced density matrix formulation of electronic structure theory. In the first scheme, an extended Fock matrix H is defined that has twice the dimension of the one-particle basis set. The corresponding Green's function, defined as the upper left block of (#omega#1-H)~(-1), yields the exact one-particle density matrix and energy. The poles of the Green's function are precisely the ionization potentials and electron affinities of the extended Koopmans theorem. In the second scheme, a generalized Fock equation [F(#rho#), #rho#]=X is derived that is satisfied by the exact non-idempotent one-particle density matrix. The antisymmetric matrix X on the right-hand side is obtained from the irreducible part of the two-particle reduced density matrix, while F is the usual Fock matrix defined using the correlated one-matrix. The generalized Fock equation is a necessary condition but does not determine #rho# uniquely. Alternatively, the one-matrix can be obtained from the irreducible part of the two-matrix directly, using a sum rule. The analysis leads to some additional desiderata and separability properties that may be imposed on traditional wave function based approaches. Possibilities for practical computational schemes are addressed briefly.
机译:考虑了两种可能的途径来获得电子结构理论的单粒子密度降低的矩阵公式。在第一种方案中,定义了扩展的Fock矩阵H,该矩阵具有单粒子基础集尺寸的两倍。相应的格林函数定义为(#omega#1-H)〜(-1)的左上块,可产生精确的单粒子密度矩阵和能量。格林函数的极点恰好是扩展的库普曼定理的电离势和电子亲和力。在第二种方案中,导出了精确的非幂等单粒子密度矩阵所满足的广义Fock方程[F(#rho#),#rho#] = X。右侧的反对称矩阵X是从两粒子密度降低矩阵的不可约部分获得的,而F是使用相关的单矩阵定义的常用Fock矩阵。广义的Fock方程是必要条件,但不能唯一地确定#rho#。或者,可以使用求和规则直接从两个矩阵的不可约部分获得一个矩阵。该分析导致一些附加的desiderata和可分离性属性,这些属性可能会强加于基于传统波动函数的方法上。简要介绍了实际计算方案的可能性。

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