SDSPT2s:SDSPT2 with Selection

IF 5.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Chemical Theory and Computation Pub Date : 2025-01-23 DOI:10.1021/acs.jctc.4c0159610.1021/acs.jctc.4c01596

Yibo Lei*, Yang Guo, Bingbing Suo and Wenjian Liu*,

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Abstract

As an approximation to SDSCI [static-dynamic-static (SDS) configuration interaction (CI), a minimal MRCI; Theor. Chem. Acc. 2014, 133, 1481], SDSPT2 [Mol. Phys. 2017, 115, 2696] is a CI-like multireference (MR) second-order perturbation theory (PT2) that treats single and multiple roots in the same manner. This feature permits the use of configuration selection over a large complete active space (CAS) P to end up with a much reduced reference space P̃, which is connected only with a small portion (Q̃₁) of the full first-order interacting space Q connected to P. The most expensive portion of the reduced interacting Q̃₁ space (which involves three active orbitals) can further be truncated by partially bypassing its generation followed by an integral-based cutoff. With marginal loss of accuracy, the selection-truncation procedure, along with an efficient evaluation and storage of internal contraction coefficients, renders SDSPT2s (SDSPT2 with selection) applicable to systems that cannot be handled by the parent CAS-based SDSPT2, as demonstrated by several challenging showcases.

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SDSPT2:SDSPT2带选择

作为SDSCI[静态-动态-静态（SDS）配置相互作用（CI）]的近似值，最小MRCI；定理。化学。SDSPT2 [Mol. Phys. 2017,115, 2696]是一种类似ci的多参考（MR）二阶摄动理论（PT2），它以相同的方式处理单根和多根。这个特征允许在一个大的完全活动空间（CAS） P上使用配置选择，最终得到一个大大减少的参考空间P，它只与连接到P的完整一阶相互作用空间Q的一小部分（Q 1）相连。减少的相互作用Q 1空间中最昂贵的部分（包括三个活动轨道）可以通过部分绕过它的生成，然后通过基于积分的截止来进一步截断。随着精度的边际损失，选择截断过程，以及内部收缩系数的有效评估和存储，使得SDSPT2 （SDSPT2带选择）适用于基于cas的父SDSPT2无法处理的系统，如几个具有挑战性的展示所示。

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来源期刊

Journal of Chemical Theory and Computation 化学-物理：原子、分子和化学物理

CiteScore

9.90

自引率

16.40%

发文量

568

审稿时长

1 months

期刊介绍： The Journal of Chemical Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere. Papers reporting new theories, methodology, and/or important applications in quantum electronic structure, molecular dynamics, and statistical mechanics are appropriate for submission to this Journal. Specific topics include advances in or applications of ab initio quantum mechanics, density functional theory, design and properties of new materials, surface science, Monte Carlo simulations, solvation models, QM/MM calculations, biomolecular structure prediction, and molecular dynamics in the broadest sense including gas-phase dynamics, ab initio dynamics, biomolecular dynamics, and protein folding. The Journal does not consider papers that are straightforward applications of known methods including DFT and molecular dynamics. The Journal favors submissions that include advances in theory or methodology with applications to compelling problems.