{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Papai M"],"funding":["Magyar Tudom?nyos Akad?mia","Nemzeti Kutat?si Fejleszt?si ?s Innov?ci?s Hivatal","Magyarorsz?g Korm?nya","European Regional Development Fund"],"pagination":["1329-1339"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC8908767"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["18(3)"],"pubmed_abstract":["A new theoretical approach is presented and applied for the simulation of Fe(II) low-spin (LS, singlet, t<sub>2g</sub><sup>6</sup>e<sub>g</sub><sup>0</sup>) → high-spin (HS, quintet, t<sub>2g</sub><sup>4</sup>e<sub>g</sub><sup>2</sup>) photoswitching dynamics of the octahedral model complex [Fe(NCH)<sub>6</sub>]<sup>2+</sup>. The utilized synergistic methodology heavily exploits the strengths of complementary electronic structure and spin-vibronic dynamics methods. Specifically, we perform 3D quantum dynamics (QD) and full-dimensional trajectory surface hopping (TSH, in conjunction with a linear vibronic coupling model), with the modes for QD selected by TSH. We follow a hybrid approach which is based on the application of time-dependent density functional theory (TD-DFT) excited-state potential energy surfaces (PESs) and multiconfigurational second-order perturbation theory (CASPT2) spin-orbit couplings (SOCs). Our method delivers accurate singlet-triplet-quintet intersystem crossing (ISC) dynamics, as assessed by comparison to our recent high-level <i>ab initio</i> simulations and related time-resolved experimental data. Furthermore, we investigate the capability of our simulations to identify the location of ISCs. Finally, we assess the approximation of constant SOCs (calculated at the Franck-Condon geometry), whose validity has central importance for the combination of TD-DFT PESs and CASPT2 SOCs. This efficient methodology will have a key role in simulating LS → HS dynamics for more complicated cases, involving higher density of states and varying electronic character, as well as the analysis of ultrafast experiments."],"journal":["Journal of chemical theory and computation"],"pubmed_title":["Toward Simulation of Fe(II) Low-Spin → High-Spin Photoswitching by Synergistic Spin-Vibronic Dynamics."],"pmcid":["PMC8908767"],"funding_grant_id":["NKFIH PD 134976","VEKOP-2.3.2-16-2017-00015"],"pubmed_authors":["Papai M"],"additional_accession":[]},"is_claimable":false,"name":"Toward Simulation of Fe(II) Low-Spin → High-Spin Photoswitching by Synergistic Spin-Vibronic Dynamics.","description":"A new theoretical approach is presented and applied for the simulation of Fe(II) low-spin (LS, singlet, t<sub>2g</sub><sup>6</sup>e<sub>g</sub><sup>0</sup>) → high-spin (HS, quintet, t<sub>2g</sub><sup>4</sup>e<sub>g</sub><sup>2</sup>) photoswitching dynamics of the octahedral model complex [Fe(NCH)<sub>6</sub>]<sup>2+</sup>. The utilized synergistic methodology heavily exploits the strengths of complementary electronic structure and spin-vibronic dynamics methods. Specifically, we perform 3D quantum dynamics (QD) and full-dimensional trajectory surface hopping (TSH, in conjunction with a linear vibronic coupling model), with the modes for QD selected by TSH. We follow a hybrid approach which is based on the application of time-dependent density functional theory (TD-DFT) excited-state potential energy surfaces (PESs) and multiconfigurational second-order perturbation theory (CASPT2) spin-orbit couplings (SOCs). Our method delivers accurate singlet-triplet-quintet intersystem crossing (ISC) dynamics, as assessed by comparison to our recent high-level <i>ab initio</i> simulations and related time-resolved experimental data. Furthermore, we investigate the capability of our simulations to identify the location of ISCs. Finally, we assess the approximation of constant SOCs (calculated at the Franck-Condon geometry), whose validity has central importance for the combination of TD-DFT PESs and CASPT2 SOCs. This efficient methodology will have a key role in simulating LS → HS dynamics for more complicated cases, involving higher density of states and varying electronic character, as well as the analysis of ultrafast experiments.","dates":{"release":"2022-01-01T00:00:00Z","publication":"2022 Mar","modification":"2025-04-04T23:34:23.668Z","creation":"2025-04-04T23:34:23.668Z"},"accession":"S-EPMC8908767","cross_references":{"pubmed":["35199532"],"doi":["10.1021/acs.jctc.1c01184"]}}