Graspg的非正交扩展——大且紧凑活性空间下的动态电子关联
Non-orthogonal extension of Graspg - dynamic electron correlation for large and compact active spaces
浏览论文内容
中文总结 AI 辅助
本文提出分区相关函数相互作用（PCFI）方法，通过非正交轨道集和双正交变换扩展Graspg，实现大且紧凑活性空间下的动态电子关联，提供更紧凑收敛和稳定性的相对论原子结构计算。
中文摘要 AI 辅助
当使用单一共同的正交轨道基时，组态态函数展开的快速增长常常限制了相关敏感原子属性的精确相对论多组态计算。在本工作中，开发了一种用于相对论原子结构计算的分区相关函数相互作用（PCFI）方法。相关空间被划分为具有物理动机的组分，这些组分使用相关特定的轨道集独立优化。通过双正交变换评估由相互非正交轨道集构建的组态空间之间的相互作用，从而允许在紧凑的最终相互作用计算中组合不同的相关效应。提供了该方法的完整细节，强调其与组态态函数生成器（CSFGs）的联系，这显著减少了传统RCI计算中构建哈密顿矩阵所需的时间。给出了对中性Li、Be和Al原子的能级、质量位移和超精细结构常数的应用。与依赖单一轨道基的传统相对论组态相互作用（RCI）计算相比，PCFI在总能量和跃迁能量上产生更紧凑和可预测的收敛模式。它还为相关敏感属性（如特定质量位移和超精细常数）提供了更高的稳定性。通过使用面向属性的分区，PCFI更有效地捕获核心极化效应，从而减少了标准RCI方法中常见的振荡行为。总体而言，结果表明PCFI为相关依赖原子属性的精确相对论多组态计算提供了一个有前景且计算高效的框架。
英文摘要
Accurate relativistic multiconfiguration calculations of correlation-sensitive atomic properties are often limited by the rapid growth of configuration state function expansions when a single common orthonormal orbital basis is used. In this work, a partitioned correlation function interaction (PCFI) method is developed for relativistic atomic structure calculations. The correlation space is separated into physically motivated components, which are optimized independently with correlation-specific orbital sets. The interactions between configuration spaces constructed from mutually non-orthogonal orbital sets are evaluated using biorthonormal transformations, allowing different correlation effects to be combined in a compact final interaction calculation. Full details of the method are provided, emphasizing its connection to configuration state function generators (CSFGs), which significantly reduce the time required to construct the Hamiltonian matrix in conventional RCI calculations. Applications to the neutral Li, Be, and Al atoms are presented for energy levels, mass shifts and hyperfine structure constants. Compared with conventional relativistic configuration interaction (RCI) calculations that rely on a single orbital basis, PCFI produces more compact and predictable convergence patterns for both total and transition energies. It also offers greater stability for correlation-sensitive properties such as specific mass shifts and hyperfine constants. By using property-oriented partitions, PCFI captures core-polarization effects more effectively, thereby reducing the oscillatory behavior often observed in standard RCI approaches. Overall, the results demonstrate that PCFI provides a promising and computationally efficient framework for accurate relativistic multiconfiguration calculations of correlation-dependent atomic properties.
发表机构
- Fudan University（复旦大学）
- Malmö University（马尔默大学）
- Vilnius University（维尔纽斯大学）
- Université libre de Bruxelles（布鲁塞尔自由大学）
机构由 AI 辅助整理，请以论文原文为准。
