Bridging the Gap between Variational and Perturbational DFT-Based Methods for Calculating Excited States.

IF 5.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Chemical Theory and Computation Pub Date : 2025-07-22 DOI:10.1021/acs.jctc.5c00724

Andrey Sinyavskiy,Momir Mališ,Sandra Luber

引用次数: 0

Abstract

A thorough investigation of the delta self-consistent field (ΔSCF) method within the restricted-open Kohn-Sham (ROKS) formalism has been carried out. The ROKS-based ΔSCF targets unmixed singlet excited electronic states, avoiding the need for a spin purification procedure. A modification of the maximum overlap method to improve the convergence of the ΔSCF method is presented, in addition to a molecular orbital tracking and order-preserving algorithm. For benchmarking purposes a large-scale comparison with time-dependent density functional theory (TDDFT) was conducted: both single- and multi-reference singlet and triplet excited electronic states of various molecules were reproduced using ΔSCF and compared to the states provided by TDDFT. Besides the excitation energies, we also compared the electron densities and the transition dipole moments of the molecules between the two methods.

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弥合变分和微扰dft计算激发态方法之间的差距。

本文对限制开放Kohn-Sham （ROKS）形式体系中的delta自洽场（ΔSCF）方法进行了深入的研究。基于roks的ΔSCF目标是未混合的单线态激发态，避免了自旋纯化过程的需要。为了提高ΔSCF方法的收敛性，提出了对最大重叠法的改进，并提出了分子轨道跟踪和保序算法。为了进行基准测试，与时间依赖密度泛函理论（TDDFT）进行了大规模比较：使用ΔSCF再现了各种分子的单参考和多参考单重态和三重态激发态，并与TDDFT提供的状态进行了比较。除了激发能外，我们还比较了两种方法的电子密度和分子的跃迁偶极矩。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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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Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere.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.