论文标题

从头算到零波函数的降低密度矩阵功能理论:沿绝热连接路径的精确和近似配方

Reduced density matrix functional theory from an ab initio seniority-zero wave function: Exact and approximate formulations along adiabatic connection paths

论文作者

Senjean, Bruno, Yalouz, Saad, Nakatani, Naoki, Fromager, Emmanuel

论文摘要

当前,基于资历概念的新方法层次结构的发展越来越兴趣,这是最近在量子化学中引入的。尽管这些方法具有巨大的潜力,但在单个和原本限制方法中,对动态和静态相关效应的准确描述仍然是一个挑战。在这项工作中,我们提出了降低密度 - 矩阵功能理论(RDMFT)的替代公式,其中(单电子还原)的密度矩阵被映射到从头开始的零零波函数上。在这一理论中,确切的自然轨道及其占用量是根据有效的零计算来自一确定的。后者涉及通用的高级密度矩阵函数,在该功能下,在与密度矩阵相关的特定约束下得出和实现了绝热连接(AC)公式。在原型氢链和氦二聚体中观察到的(约束)AC积分的明显曲率表明,在这种情况下,二阶扰动理论中高含量相关性的描述是不足的。在AC上应用多个线性插值或将二阶扰动理论连接到通过Padé近似值的全率处理是更好的策略。预计此类信息将在未来的高级密度 - 密度 - 矩阵功能近似值的设计中提供指南。

Currently, there is a growing interest in the development of a new hierarchy of methods based on the concept of seniority, which has been introduced quite recently in quantum chemistry. Despite the enormous potential of these methods, the accurate description of both dynamical and static correlation effects within a single and in-principle-exact approach remains a challenge. In this work, we propose an alternative formulation of reduced density-matrix functional theory (RDMFT) where the (one-electron reduced) density matrix is mapped onto an ab initio seniority-zero wave function. In this theory, the exact natural orbitals and their occupancies are determined self-consistently from an effective seniority-zero calculation. The latter involves a universal higher-seniority density matrix functional for which an adiabatic connection (AC) formula is derived and implemented under specific constraints that are related to the density matrix. The pronounced curvature of the (constrained) AC integrand, which is numerically observed in prototypical hydrogen chains and the Helium dimer, indicates that a description of higher-seniority correlations within second-order perturbation theory is inadequate in this context. Applying multiple linear interpolations along the AC or connecting second-order perturbation theory to a full-seniority treatment via Padé approximants are better strategies. Such information is expected to serve as a guide in the future design of higher-seniority density-matrix functional approximations.

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