发表机构
North Carolina State University（北卡罗来纳州立大学）
机构由 AI 辅助整理，请以论文原文为准。AI 中文总结
本研究扩展ccECP库，为5d和6p重元素开发半局域赝势，采用分层核-价划分策略，实现高原子精度和分子可转移性，并提升量子蒙特卡洛数值稳定性。
AI 中文摘要
我们通过开发半局域赝势及匹配的基组，扩展了相关一致有效核势（ccECPs）库，涵盖$5d$（Hf、Os、Hg）和$6p$（Tl、Po、At、Rn）块的重元素。为了准确捕捉标量相对论效应、自旋-轨道耦合和电子-电子关联，我们实施了跨三种不同分辨率的分层核-价划分策略。这包括一个小的60核（Hf、Os、Hg）定义，显式关联亚价壳层；一个大的78核定义用于主族元素，严格考虑稀疏价环境中的核极化和弛豫效应；以及一个中间的68核划分用于Hg和Tl。这种68核架构代表了ccECP库中的独特发展，以对较轻元素未探索的方式优化了精度与计算效率之间的平衡。针对相对论全电子CCSD(T)参考进行优化，ccECPs展现出卓越的原子精度，全局平均原子低激发态偏差仅为0.045 eV。这一精度直接转化为稳健的分子可转移性，系统地将解离能差异限制在0.03 eV以下，平衡键长在0.005 Å以内。通过在原点实施正则化有限势以增强随机量子蒙特卡洛方法中的数值稳定性，该库消除了重元素系统及材料预测性多体模拟的关键方法论瓶颈。
英文摘要
We expand the correlation-consistent effective core potentials (ccECPs) library by developing semi-local pseudopotentials and matching basis sets by heavy-elements from $5d$ (Hf, Os, Hg) and $6p$ (Tl, Po, At, Rn) blocks. In order to accurately capture scalar relativistic effects, spin-orbit coupling, and electron-electron correlation, we implement a tiered core-valence partitioning strategy across three distinct resolutions. This includes a small 60-core (Hf, Os, Hg) that explicitly correlates subvalence shells, a large 78-core definition for the main-group elements that rigorously accounts for core polarization and relaxation effects in sparse valence environments, and an intermediate 68-core partition for Hg and Tl. This 68-core architecture represents a unique development in the ccECP library, optimizing the balance between accuracy and computational efficiency in a manner unexplored for ligther elements. Optimized against relativistic all-electron CCSD(T) references, the ccECPs deliver outstanding atomic precision, achieving a global average atomic low-lying states deviation of just 0.045 eV. This accuracy translates directly to robust molecular transferability, systematically restricting dissociation energy discrepancies to under 0.03 eV, equilibrium bond lengths to within 0.005 Å. By enforcing a regularized, finite potential at the origin for enhanced numerical stability in stochastic quantum Monte Carlo methods, this library removes a critical methodological bottleneck for predictive many-body simulations of heavy-element systems and materials.
Comments18 pages, 14 figures, 3 tables. To be published in the Journal of Chemical Physics
