{"title":"Reliable Diradical Characterization via Precise Singlet-Triplet Gap Calculations: Application to Thiele, Chichibabin, and Müller Analogous Diradicals.","authors":"Qi Sun, Jean-Luc Brédas, Hong Li","doi":"10.1021/acs.jctc.4c01384","DOIUrl":null,"url":null,"abstract":"<p><p>Accurately calculating the diradical character (<i>y</i><sub>0</sub>) of molecular systems remains a significant challenge due to the scarcity of experimental data and the inherent multireference nature of the electronic structure. In this study, various quantum mechanical approaches, including broken symmetry density functional theory (BS-DFT), spin-flip time-dependent density functional theory (SF-TDDFT), mixed-reference spin-flip time-dependent density functional theory (MRSF-TDDFT), complete active space self-consistent field (CASSCF), complete active space second-order perturbation theory (CASPT2), and multiconfigurational pair-density functional theory (MCPDFT), are employed to compute the singlet-triplet energy gaps (<i>E</i><sub>ST</sub>) and <i>y</i><sub>0</sub> values in Thiele, Chichibabin, and Müller analogous diradicals. By systematically comparing the results from these computational methods, we identify optimally tuned long-range corrected functional CAM-B3LYP in the BS-DFT framework as a most efficient method for accurately and affordably predicting both <i>E</i><sub>ST</sub> and <i>y</i><sub>0</sub> values. Additionally, our results demonstrate that (i) MRSF-TDDFT performs much better than SF-TDDFT; (ii) the MCPDFT method is robust in determining <i>E</i><sub>ST</sub> with minimal dependence on the choice of active space. These findings provide insight into the electronic structure and diradical character of the investigated molecules and highlight effective computational strategies for future studies in this domain. Thus, this work not only advances our understanding of diradical systems but also offers practical guidelines for their computational investigation.</p>","PeriodicalId":45,"journal":{"name":"Journal of Chemical Theory and Computation","volume":" ","pages":""},"PeriodicalIF":5.7000,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Theory and Computation","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.jctc.4c01384","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Accurately calculating the diradical character (y0) of molecular systems remains a significant challenge due to the scarcity of experimental data and the inherent multireference nature of the electronic structure. In this study, various quantum mechanical approaches, including broken symmetry density functional theory (BS-DFT), spin-flip time-dependent density functional theory (SF-TDDFT), mixed-reference spin-flip time-dependent density functional theory (MRSF-TDDFT), complete active space self-consistent field (CASSCF), complete active space second-order perturbation theory (CASPT2), and multiconfigurational pair-density functional theory (MCPDFT), are employed to compute the singlet-triplet energy gaps (EST) and y0 values in Thiele, Chichibabin, and Müller analogous diradicals. By systematically comparing the results from these computational methods, we identify optimally tuned long-range corrected functional CAM-B3LYP in the BS-DFT framework as a most efficient method for accurately and affordably predicting both EST and y0 values. Additionally, our results demonstrate that (i) MRSF-TDDFT performs much better than SF-TDDFT; (ii) the MCPDFT method is robust in determining EST with minimal dependence on the choice of active space. These findings provide insight into the electronic structure and diradical character of the investigated molecules and highlight effective computational strategies for future studies in this domain. Thus, this work not only advances our understanding of diradical systems but also offers practical guidelines for their computational investigation.
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.