Second-Order Moller-Plesset Perturbation (MP2) Theory at Finite Temperature: Relation with Surjan's Density Matrix MP2 and Its Application to Linear-Scaling Divide-and-Conquer Method
Second-Order Moller-Plesset Perturbation (MP2) Theory at Finite Temperature: Relation with Surjan's Density Matrix MP2 and Its Application to Linear-Scaling Divide-and-Conquer Method
复制标题
有限温度下的二阶 Moller-Plesset 微扰 (MP2) 理论：与 Surjan 密度矩阵 MP2 的关系及其在线性标度分治法中的应用
DOI：
10.1007/s00214-015-1710-y
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
T. Taketsugu
中科院分区：
文献类型：
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作者：
M. Kobayashi;T. Taketsugu
2005年，Surján给出了两个显式公式，用于评估二阶Møller-Plesset微扰（MP2）能量作为Hartree-Fock密度矩阵$$\varvec{D}$$的函数（Chem Phys Lett 406:318, 2005），它们被称为$$\Delta E_\text {MP2}[\varvec{D}]$$泛函。本文给出了FT Hartree-Fock密度矩阵的有限温度MP2能量泛函。FT-MP2也有两种公式，即常规公式和重整公式；后者是Hirata和He最近制定的（J Chem Phys 138:204112, 2013）。证明了两个FT-MP2的公式与$$\Delta E_\text {MP2}[\varvec{D}]$$泛函之间存在一一对应关系。这一事实可以解释当近似Hartree-Fock密度矩阵被应用时，两个$$\Delta E_\text {MP2}[\varvec{D}]$$函数的不同行为，这是由Kobayashi和Nakai先前研究的（Chem Phys Lett 420:250, 2006）。我们还将FT-MP2形式化应用于线性缩放分治法，以通过微小的计算工作量来提高精度。
In 2005, Surján showed two explicit formulas for evaluating the second-order Møller–Plesset perturbation (MP2) energy as a functional of the Hartree–Fock density matrix $$\varvec{D}$$ (Chem Phys Lett 406:318, 2005), which are referred to as the $$\Delta E_\text {MP2}[\varvec{D}]$$ functionals. In this paper, we present the finite-temperature (FT) MP2 energy functionals of the FT Hartree–Fock density matrix. There are also two formulas for the FT-MP2, namely the conventional and renormalized ones; the latter of which has recently been formulated by Hirata and He (J Chem Phys 138:204112, 2013). We proved that there exists one-to-one correspondence between the formulas of two FT-MP2 and the $$\Delta E_\text {MP2}[\varvec{D}]$$ functionals. This fact can explain the different behavior of two $$\Delta E_\text {MP2}[\varvec{D}]$$ functionals when an approximate Hartree–Fock density matrix is applied, which was previously investigated by Kobayashi and Nakai (Chem Phys Lett 420:250, 2006). We also applied the FT-MP2 formalisms to the linear-scaling divide-and-conquer method for improving the accuracy with tiny addition of the computational efforts.