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交流:一种新型的计算 MP2 相关能量的方法,不考虑基组叠加误差和完全基组外推。

Communication: A novel implementation to compute MP2 correlation energies without basis set superposition errors and complete basis set extrapolation.

机构信息

Université de Lorraine, CRM, UMR 7036, 54506 Vandoeuvre-lès-Nancy, France.

出版信息

J Chem Phys. 2017 Jun 7;146(21):211102. doi: 10.1063/1.4985096.

Abstract

By using a formulation based on the dynamical polarizability, we propose a novel implementation of second-order Møller-Plesset perturbation (MP2) theory within a plane wave (PW) basis set. Because of the intrinsic properties of PWs, this method is not affected by basis set superposition errors. Additionally, results are converged without relying on complete basis set extrapolation techniques; this is achieved by using the eigenvectors of the static polarizability as an auxiliary basis set to compactly and accurately represent the response functions involved in the MP2 equations. Summations over the large number of virtual states are avoided by using a formalism inspired by density functional perturbation theory, and the Lanczos algorithm is used to include dynamical effects. To demonstrate this method, applications to three weakly interacting dimers are presented.

摘要

我们基于动力学极化率提出了一种新的在平面波(PW)基组中实现二级 Møller-Plesset 微扰(MP2)理论的方法。由于 PW 的固有特性,该方法不受基组叠加误差的影响。此外,结果无需依赖完全基组外推技术即可收敛;这是通过使用静态极化率的特征向量作为辅助基组来紧凑和准确地表示 MP2 方程中涉及的响应函数来实现的。通过受密度泛函微扰理论启发的形式避免了对大量虚拟态的求和,并且使用 Lanczos 算法来包括动力学效应。为了验证该方法,我们对三个弱相互作用的二聚体进行了应用。

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