{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,5,8]],"date-time":"2026-05-08T12:13:45Z","timestamp":1778242425034,"version":"3.51.4"},"reference-count":48,"publisher":"AIP Publishing","issue":"18","funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22303053"],"award-info":[{"award-number":["22303053"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2026,5,14]]},"abstract":"<jats:p>Ultrafast exciton localization in molecular crystals plays an essential role in the solid-state photochemical reactions. Studying exciton dynamics that convert separate electrons and holes into a molecular excited state is challenging because it requires a computational approach that bridges condensed-phase and molecular electronic structure theories. In this work, we take advantage of the periodic time-dependent density functional theory to investigate the exciton localization dynamics in three molecular crystals, 1,2-bis(4-(anthracen-9-yl)phenyl)diazene (1), 1-methylimidazoyl enone (2), and 3-azido-1-(4-chlorophenyl)propenone (3), undergoing typical photochemical isomerization, [2 + 2]-cycloaddition, and dissociation. Our calculations showed delocalized \u03c0\u03c0*-type electron and hole distributions during vertical excitation of ground-state molecular crystals. The S1-state geometry optimization revealed a partially localized exciton across multiple molecules in the crystals. Comprehensive S1 dynamics simulations uncovered the system-dependent role of exciton localization: (1) the exciton in molecular crystal 1 showed an intermolecular charge-transfer from the neighboring anthracene and azobenzene groups, where the hole on the anthracene groups moved around the electron at central azobenzene; (2) the exciton dynamics in molecular crystal 2 showed competing exciton transportation and localization, where electron and hole separate or combine via the \u03c0\u03c0-stacking; and (3) the exciton in molecular crystal 3 showed dominant intramolecular CT, while the close-packing still generates a competing intermolecular CT between a dimer. These findings provide a fundamental understanding of exciton dynamics in photochemically reactive molecular crystals, paving the way for improving simulations of solid-state photochemical reactions.<\/jats:p>","DOI":"10.1063\/5.0320259","type":"journal-article","created":{"date-parts":[[2026,5,8]],"date-time":"2026-05-08T11:46:36Z","timestamp":1778240796000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":0,"title":["Ultrafast dynamics of exciton localization in photochemically reactive molecular crystals"],"prefix":"10.1063","volume":"164","author":[{"ORCID":"https:\/\/orcid.org\/0009-0001-6499-2745","authenticated-orcid":false,"given":"Xia","family":"Lei","sequence":"first","affiliation":[{"name":"Department of Materials Science and Engineering, Southern University of Science and Technology 1 , Shenzhen 518055,","place":["China"]},{"name":"Hoffmann Institute of Advanced Materials, Shenzhen Polytechnic University 2 , Shenzhen 518055,","place":["China"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6970-9080","authenticated-orcid":false,"given":"Xingyu","family":"Luo","sequence":"additional","affiliation":[{"name":"Hoffmann Institute of Advanced Materials, Shenzhen Polytechnic University 2 , Shenzhen 518055,","place":["China"]},{"name":"Postdoctoral Innovation Practice Base, Shenzhen Polytechnic University 3 , Shenzhen 518055,","place":["China"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2868-0613","authenticated-orcid":false,"given":"Baomin","family":"Xu","sequence":"additional","affiliation":[{"name":"Department of Materials Science and Engineering, Southern University of Science and Technology 1 , Shenzhen 518055,","place":["China"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4743-0318","authenticated-orcid":false,"given":"Jingbai","family":"Li","sequence":"additional","affiliation":[{"name":"Hoffmann Institute of Advanced Materials, Shenzhen Polytechnic University 2 , Shenzhen 518055,","place":["China"]}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"317","published-online":{"date-parts":[[2026,5,8]]},"reference":[{"key":"2026050807463268300_c1","doi-asserted-by":"publisher","first-page":"215095","DOI":"10.1016\/j.ccr.2023.215095","article-title":"Cocrystals for photochemical solid-state reactions: An account on crystal engineering perspective","volume":"483","year":"2023","journal-title":"Coord. Chem. Rev."},{"issue":"6","key":"2026050807463268300_c2","doi-asserted-by":"publisher","first-page":"834","DOI":"10.1021\/acscentsci.5c00549","article-title":"In crystallo photochemistry: Reimagining synthetic tractability with transparent single-crystalline flasks","volume":"11","year":"2025","journal-title":"ACS Cent. Sci."},{"issue":"22","key":"2026050807463268300_c3","doi-asserted-by":"publisher","first-page":"14948","DOI":"10.1021\/jacs.4c04706","article-title":"A general synthetic strategy toward the truxillate natural products via solid-state photocycloadditions","volume":"146","year":"2024","journal-title":"J.\u00a0Am. Chem. Soc."},{"issue":"2","key":"2026050807463268300_c4","doi-asserted-by":"publisher","first-page":"1717","DOI":"10.1021\/acs.chemrev.1c00247","article-title":"Strategic use of visible-light photoredox catalysis in natural product synthesis","volume":"122","year":"2022","journal-title":"Chem. Rev."},{"issue":"17","key":"2026050807463268300_c5","doi-asserted-by":"publisher","first-page":"9683","DOI":"10.1021\/acs.chemrev.5b00760","article-title":"Photochemical approaches to complex chemotypes: Applications in natural product synthesis","volume":"116","year":"2016","journal-title":"Chem. Rev."},{"issue":"12","key":"2026050807463268300_c6","doi-asserted-by":"publisher","first-page":"6915","DOI":"10.1021\/acs.chemrev.0c01212","article-title":"Photoclick chemistry: A bright idea","volume":"121","year":"2021","journal-title":"Chem. Rev."},{"issue":"1","key":"2026050807463268300_c7","doi-asserted-by":"publisher","first-page":"7112","DOI":"10.1038\/s41467-022-34833-1","article-title":"Photocatalytic direct borylation of carboxylic acids","volume":"13","year":"2022","journal-title":"Nat. Commun."},{"issue":"26","key":"2026050807463268300_c8","doi-asserted-by":"publisher","first-page":"31787","DOI":"10.1021\/acsami.3c04631","article-title":"Understanding solid-state photochemical energy storage in polymers with azobenzene side groups","volume":"15","year":"2023","journal-title":"ACS Appl. Mater. Interfaces"},{"issue":"17","key":"2026050807463268300_c9","doi-asserted-by":"publisher","first-page":"7313","DOI":"10.1039\/d1cs00890k","article-title":"Status and challenges for molecular solar thermal energy storage system based devices","volume":"51","year":"2022","journal-title":"Chem. Soc. Rev."},{"issue":"8","key":"2026050807463268300_c10","doi-asserted-by":"publisher","first-page":"1478","DOI":"10.1021\/acs.accounts.0c00235","article-title":"Engineering of norbornadiene\/quadricyclane photoswitches for molecular solar thermal energy storage applications","volume":"53","year":"2020","journal-title":"Acc. Chem. Res."},{"issue":"1","key":"2026050807463268300_c11","doi-asserted-by":"publisher","first-page":"6647","DOI":"10.1038\/s41467-025-61723-z","article-title":"A solid-solution approach for controllable photomechanical crystalline materials","volume":"16","year":"2025","journal-title":"Nat. Commun."},{"issue":"47","key":"2026050807463268300_c12","doi-asserted-by":"publisher","first-page":"32757","DOI":"10.1021\/jacs.4c12670","article-title":"Photochemical reaction front propagation and control in molecular crystals","volume":"146","year":"2024","journal-title":"J.\u00a0Am. Chem. Soc."},{"issue":"36","key":"2026050807463268300_c13","doi-asserted-by":"publisher","first-page":"25028","DOI":"10.1021\/jacs.4c07453","article-title":"Photodimerization-triggered photopolymerization of triene coordination polymers enables macroscopic photomechanical movements","volume":"146","year":"2024","journal-title":"J.\u00a0Am. Chem. Soc."},{"issue":"2","key":"2026050807463268300_c14","doi-asserted-by":"publisher","first-page":"183","DOI":"10.1021\/accountsmr.4c00325","article-title":"Photoresponsive coordination polymer single crystal platforms: Design and applications","volume":"6","year":"2025","journal-title":"Acc. Mater. Res."},{"issue":"21","key":"2026050807463268300_c15","doi-asserted-by":"publisher","first-page":"17772","DOI":"10.1021\/jacs.5c01145","article-title":"Regulating reversible untwisting and twisting motions in helical dynamic molecular crystals","volume":"147","year":"2025","journal-title":"J.\u00a0Am. Chem. Soc."},{"issue":"9","key":"2026050807463268300_c16","doi-asserted-by":"publisher","first-page":"8487","DOI":"10.1021\/acs.chemrev.1c00648","article-title":"Dynamics of excitons in conjugated molecules and organic semiconductor systems","volume":"122","year":"2022","journal-title":"Chem. Rev."},{"issue":"26","key":"2026050807463268300_c17","doi-asserted-by":"publisher","first-page":"4191","DOI":"10.1021\/acs.jpca.2c02354","article-title":"Excited states of metal-adsorbed dimethyl disulfide: A TDDFT study with cluster model","volume":"126","year":"2022","journal-title":"J.\u00a0Phys. Chem. A"},{"issue":"14","key":"2026050807463268300_c18","doi-asserted-by":"publisher","first-page":"5490","DOI":"10.1021\/acs.jpclett.0c01247","article-title":"On-surface chemistry induced by long-lived excitons: (NO)2 dissociation on C60","volume":"11","year":"2020","journal-title":"J.\u00a0Phys. Chem. Lett."},{"issue":"15","key":"2026050807463268300_c19","doi-asserted-by":"publisher","first-page":"6587","DOI":"10.1021\/acs.jctc.4c00539","article-title":"Nonadiabatic exciton dynamics and energy gradients in the framework of FMO-LC-TDDFTB","volume":"20","year":"2024","journal-title":"J.\u00a0Chem. Theory Comput."},{"issue":"12","key":"2026050807463268300_c20","doi-asserted-by":"publisher","first-page":"5366","DOI":"10.1021\/ct500765m","article-title":"Ab initio implementation of the Frenkel\u2013Davydov exciton model: A naturally parallelizable approach to computing collective excitations in crystals and aggregates","volume":"10","year":"2014","journal-title":"J.\u00a0Chem. Theory Comput."},{"issue":"1","key":"2026050807463268300_c21","doi-asserted-by":"publisher","first-page":"6613","DOI":"10.1038\/s41467-023-42067-y","article-title":"Multi-scale molecular dynamics simulations of enhanced energy transfer in organic molecules under strong coupling","volume":"14","year":"2023","journal-title":"Nat. Commun."},{"issue":"15","key":"2026050807463268300_c22","doi-asserted-by":"publisher","first-page":"6470","DOI":"10.1021\/acs.jctc.4c00493","article-title":"TD-DMRG study of exciton dynamics with both thermal and static disorders for Fenna-Matthews-Olson complex","volume":"20","year":"2024","journal-title":"J.\u00a0Chem. Theory Comput."},{"issue":"12","key":"2026050807463268300_c23","doi-asserted-by":"publisher","first-page":"7373","DOI":"10.1021\/acs.jctc.1c00942","article-title":"Surface hopping dynamics with the Frenkel exciton model in a semiempirical framework","volume":"17","year":"2021","journal-title":"J.\u00a0Chem. Theory Comput."},{"issue":"28","key":"2026050807463268300_c24","doi-asserted-by":"publisher","first-page":"13678","DOI":"10.1021\/acs.jpcc.3c02148","article-title":"Exciton localization and transfer in azobenzene aggregates: A surface hopping molecular dynamics study","volume":"127","year":"2023","journal-title":"J.\u00a0Phys. Chem. C"},{"issue":"7","key":"2026050807463268300_c25","doi-asserted-by":"publisher","first-page":"6208","DOI":"10.1021\/acsnano.2c08579","article-title":"On-the-fly nonadiabatic dynamics simulations of single-walled carbon nanotubes with covalent defects","volume":"17","year":"2023","journal-title":"ACS Nano"},{"issue":"3","key":"2026050807463268300_c26","doi-asserted-by":"publisher","first-page":"965","DOI":"10.1021\/acs.jctc.2c01044","article-title":"Machine learning exciton Hamiltonians in light-harvesting complexes","volume":"19","year":"2023","journal-title":"J.\u00a0Chem. Theory Comput."},{"issue":"14","key":"2026050807463268300_c27","doi-asserted-by":"publisher","first-page":"6160","DOI":"10.1021\/acs.jctc.4c00220","article-title":"Nonadiabatic simulation of exciton dynamics in organic semiconductors using neural network-based Frenkel Hamiltonian and gradients","volume":"20","year":"2024","journal-title":"J.\u00a0Chem. Theory Comput."},{"issue":"1","key":"2026050807463268300_c28","doi-asserted-by":"publisher","first-page":"1194","DOI":"10.1038\/s41467-025-56480-y","article-title":"Machine learning photodynamics decode multiple singlet fission channels in pentacene crystal","volume":"16","year":"2025","journal-title":"Nat. Commun."},{"issue":"6","key":"2026050807463268300_c29","doi-asserted-by":"publisher","first-page":"4496","DOI":"10.1021\/cr3004899","article-title":"Theoretical insights into photoinduced charge transfer and catalysis at oxide interfaces","volume":"113","year":"2013","journal-title":"Chem. Rev."},{"issue":"16","key":"2026050807463268300_c30","doi-asserted-by":"publisher","first-page":"163001","DOI":"10.1103\/physrevlett.95.163001","article-title":"Trajectory surface hopping in the time-dependent Kohn-Sham approach for electron-nuclear dynamics","volume":"95","year":"2005","journal-title":"Phys. Rev. Lett."},{"key":"2026050807463268300_c31","doi-asserted-by":"publisher","first-page":"eabf3759","DOI":"10.1126\/sciadv.abf3759","article-title":"Real-time GW-BSE investigations on spin-valley exciton dynamics in monolayer transition metal dichalcogenide","volume":"7","year":"2021","journal-title":"Sci. Adv."},{"issue":"2","key":"2026050807463268300_c32","doi-asserted-by":"publisher","first-page":"024105","DOI":"10.1063\/5.0248228","article-title":"Machine learning accelerated nonadiabatic dynamics simulations of materials with excitonic effects","volume":"162","year":"2025","journal-title":"J.\u00a0Chem. Phys."},{"issue":"15","key":"2026050807463268300_c33","doi-asserted-by":"publisher","first-page":"154116","DOI":"10.1063\/5.0085759","article-title":"Surface hopping dynamics in periodic solid-state materials with a linear vibronic coupling model","volume":"156","year":"2022","journal-title":"J.\u00a0Chem. Phys."},{"issue":"26","key":"2026050807463268300_c34","doi-asserted-by":"publisher","first-page":"eabg0869","DOI":"10.1126\/sciadv.abg0869","article-title":"Nuclear dynamics of singlet exciton fission in pentacene single crystals","volume":"7","year":"2021","journal-title":"Sci. Adv."},{"issue":"20","key":"2026050807463268300_c35","doi-asserted-by":"publisher","first-page":"10474","DOI":"10.1021\/acs.jctc.5c01082","article-title":"A density functional theory and semiempirical framework for trajectory surface hopping on extended systems","volume":"21","year":"2025","journal-title":"J.\u00a0Chem. Theory Comput."},{"issue":"18","key":"2026050807463268300_c36","doi-asserted-by":"publisher","first-page":"8152","DOI":"10.1021\/acs.jctc.4c00906","article-title":"Reference CC3 excitation energies for organic chromophores: Benchmarking TD-DFT, BSE\/GW, and wave function methods","volume":"20","year":"2024","journal-title":"J.\u00a0Chem. Theory Comput."},{"issue":"14","key":"2026050807463268300_c37","doi-asserted-by":"publisher","first-page":"144115","DOI":"10.1063\/5.0203818","article-title":"Assessing the accuracy of TD-DFT excited-state geometries through optimal tuning with GW energy levels","volume":"160","year":"2024","journal-title":"J.\u00a0Chem. Phys."},{"issue":"11","key":"2026050807463268300_c38","doi-asserted-by":"publisher","first-page":"6779","DOI":"10.1021\/acs.jctc.2c00531","article-title":"Quasiparticle self-consistent GW-Bethe\u2013Salpeter equation calculations for large chromophoric systems","volume":"18","year":"2022","journal-title":"J.\u00a0Chem. Theory Comput."},{"issue":"3","key":"2026050807463268300_c39","doi-asserted-by":"publisher","first-page":"1022","DOI":"10.1039\/c7cs00049a","article-title":"The Bethe\u2013Salpeter equation in chemistry: Relations with TD-DFT, applications and challenges","volume":"47","year":"2018","journal-title":"Chem. Soc. Rev."},{"issue":"28","key":"2026050807463268300_c40","doi-asserted-by":"publisher","first-page":"13051","DOI":"10.1021\/acs.jpcc.5c02605","article-title":"Assessing nonperiodic and periodic TD-DFT: The case of photochromism in aluminosilicates","volume":"129","year":"2025","journal-title":"J.\u00a0Phys. Chem. C"},{"issue":"39","key":"2026050807463268300_c41","doi-asserted-by":"publisher","first-page":"21751","DOI":"10.1021\/acs.jpcc.0c06885","article-title":"From isolated porphyrin ligands to periodic Al-PMOF: A comparative study of the optical properties using DFT\/TDDFT","volume":"124","year":"2020","journal-title":"J.\u00a0Phys. Chem. C"},{"issue":"4","key":"2026050807463268300_c42","doi-asserted-by":"publisher","first-page":"1879","DOI":"10.1021\/acs.jctc.4c01515","article-title":"Development of real-time TDDFT program with k-point sampling and DFT + U in a Gaussian and plane waves framework","volume":"21","year":"2025","journal-title":"J.\u00a0Chem. Theory Comput."},{"issue":"32","key":"2026050807463268300_c43","doi-asserted-by":"publisher","first-page":"7313","DOI":"10.1021\/acs.jpca.5c02969","article-title":"Exploring excited-state electronic structure, spectroscopy, and nonadiabatic dynamics with CP2K\u2019s multifaceted approach","volume":"129","year":"2025","journal-title":"J.\u00a0Phys. Chem. A"},{"issue":"42","key":"2026050807463268300_c44","doi-asserted-by":"publisher","first-page":"28961","DOI":"10.1021\/jacs.4c09784","article-title":"Lighting up nonemissive azobenzene derivatives by pressure","volume":"146","year":"2024","journal-title":"J.\u00a0Am. Chem. Soc."},{"issue":"43","key":"2026050807463268300_c45","doi-asserted-by":"publisher","first-page":"18565","DOI":"10.1021\/jacs.0c07830","article-title":"Cracking under internal pressure: Photodynamic behavior of vinyl azide crystals through N2 release","volume":"142","year":"2020","journal-title":"J.\u00a0Am. Chem. Soc."},{"issue":"2","key":"2026050807463268300_c46","doi-asserted-by":"publisher","first-page":"e70019","DOI":"10.1002\/wcms.70019","article-title":"Software update: The ORCA program system\u2014Version 6.0","volume":"15","year":"2025","journal-title":"Wiley Interdiscip. Rev.: Comput. Mol. Sci."},{"issue":"19","key":"2026050807463268300_c47","doi-asserted-by":"publisher","first-page":"194103","DOI":"10.1063\/5.0007045","article-title":"CP2K: An electronic structure and molecular dynamics software package\u2014Quickstep: Efficient and accurate electronic structure calculations","volume":"152","year":"2020","journal-title":"J.\u00a0Chem. Phys."},{"issue":"2","key":"2026050807463268300_c48","doi-asserted-by":"publisher","first-page":"710","DOI":"10.1021\/acs.jctc.7b01145","article-title":"Benchmarking excited-state calculations using exciton properties","volume":"14","year":"2018","journal-title":"J.\u00a0Chem. Theory Comput."}],"container-title":["The Journal of Chemical Physics"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.aip.org\/aip\/jcp\/article-pdf\/doi\/10.1063\/5.0320259\/20997655\/184501_1_5.0320259.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.aip.org\/aip\/jcp\/article-pdf\/doi\/10.1063\/5.0320259\/20997655\/184501_1_5.0320259.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,5,8]],"date-time":"2026-05-08T11:46:37Z","timestamp":1778240797000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.aip.org\/jcp\/article\/164\/18\/184501\/3389237\/Ultrafast-dynamics-of-exciton-localization-in"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,5,8]]},"references-count":48,"journal-issue":{"issue":"18","published-print":{"date-parts":[[2026,5,14]]}},"URL":"https:\/\/doi.org\/10.1063\/5.0320259","relation":{},"ISSN":["0021-9606","1089-7690"],"issn-type":[{"value":"0021-9606","type":"print"},{"value":"1089-7690","type":"electronic"}],"subject":[],"published-other":{"date-parts":[[2026,5,14]]},"published":{"date-parts":[[2026,5,8]]},"article-number":"184501"}}