Korona Tatiana
Faculty of Chemistry, University of Warsaw, Pasteura 1, Warsaw, 02-093, Poland.
Phys Chem Chem Phys. 2008 Nov 21;10(43):6509-19. doi: 10.1039/b807329e. Epub 2008 Sep 26.
A new formulation of the second-order exchange-induction energy of symmetry-adapted perturbation theory is presented. In the proposed formalism the exchange-induction energy is expressed through one- and two-particle reduced density matrices of monomers, which are of zeroth and first order with respect to the effective electrostatic potential of another monomer. The resulting expression is further modified by using the partition of two-particle density matrices into the antisymmetrized product of one-particle density matrices and the remaining cumulant part. The proposed formalism has been applied to the case of closed-shell monomers and for density matrices obtained from the expectation-value expression with coupled cluster singles and doubles wave functions. The performance of the new approach has been demonstrated on several benchmark van der Waals systems, including dimers of argon, water, and ethyne.
提出了一种对称适配微扰理论二阶交换诱导能的新形式。在所提出的形式体系中，交换诱导能通过单体的单粒子和双粒子约化密度矩阵来表示，这些矩阵相对于另一个单体的有效静电势为零阶和一阶。通过将双粒子密度矩阵划分为单粒子密度矩阵的反对称积和其余的累积量部分，对所得表达式进行了进一步修改。所提出的形式体系已应用于闭壳层单体的情况以及从具有耦合簇单双激发波函数的期望值表达式获得的密度矩阵。新方法的性能已在几个基准范德华体系上得到验证，包括氩、水和乙炔的二聚体。
