{"title":"Accurate Theoretical Assessment of MLCT Transitions in [M(Terpy)2]2+ (M = Fe, Ru, Os) Complexes","authors":"Aleksandr A. Chamkin, Elena S. Chamkina","doi":"10.1002/jcc.70227","DOIUrl":null,"url":null,"abstract":"<div>\n \n <p>The present study guides reliable and cost-effective computational approaches to metal-to-ligand charge transfer (MLCT) transitions in model [M(terpy)<sub>2</sub>]<sup>2+</sup> (M = Fe, Ru, Os) complexes relevant to electrochromic applications. We evaluated the performance of multireference perturbation theories (NEVPT2 and CASPT2), DLPNO-STEOM-CCSD, ADC(2), and 44 density functionals within TD-DFT for calculating vertical MLCT excitation energies in these systems. Multireference methods provide the most consistent agreement with experimental absorption maxima. The best theoretical estimates were obtained at the X2C NEVPT(14, 13)/x2c-QZVPPall level (2.368, 2.710, and 2.684 eV for M = Fe, Ru, and Os, respectively). DLPNO-STEOM-CCSD fails for [Fe(terpy)<sub>2</sub>]<sup>2+</sup>, presumably due to its multireference character. Among DFT functionals, local meta-GGAs such as r<sup>2</sup>SCAN offer the best trade-off between accuracy and computational cost.</p>\n </div>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 24","pages":""},"PeriodicalIF":4.8000,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Computational Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/jcc.70227","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
The present study guides reliable and cost-effective computational approaches to metal-to-ligand charge transfer (MLCT) transitions in model [M(terpy)2]2+ (M = Fe, Ru, Os) complexes relevant to electrochromic applications. We evaluated the performance of multireference perturbation theories (NEVPT2 and CASPT2), DLPNO-STEOM-CCSD, ADC(2), and 44 density functionals within TD-DFT for calculating vertical MLCT excitation energies in these systems. Multireference methods provide the most consistent agreement with experimental absorption maxima. The best theoretical estimates were obtained at the X2C NEVPT(14, 13)/x2c-QZVPPall level (2.368, 2.710, and 2.684 eV for M = Fe, Ru, and Os, respectively). DLPNO-STEOM-CCSD fails for [Fe(terpy)2]2+, presumably due to its multireference character. Among DFT functionals, local meta-GGAs such as r2SCAN offer the best trade-off between accuracy and computational cost.
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This distinguished journal publishes articles concerned with all aspects of computational chemistry: analytical, biological, inorganic, organic, physical, and materials. The Journal of Computational Chemistry presents original research, contemporary developments in theory and methodology, and state-of-the-art applications. Computational areas that are featured in the journal include ab initio and semiempirical quantum mechanics, density functional theory, molecular mechanics, molecular dynamics, statistical mechanics, cheminformatics, biomolecular structure prediction, molecular design, and bioinformatics.
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