Autor segons l'article: López, X; Straatsma, TP; Sánchez-Mansilla, A; de Graaf, C
Departament: Química Física i Inorgànica
Autor/s de la URV: De Graaf, Cornelis / López Fernández, Javier / Sánchez Mansilla, Aitor María
Paraules clau: Transition Total-energy calculations States Initio molecular-dynamics Efficiency
Resum: The present computational work analyzes singlet fission(SF) asa pathway for multiplication of photogenerated excitons in crystallinepolyacenes. Our study explores the well-known crystalline pentacene(C22H14) and the prospective and potentiallyinteresting doped B,N-pentacene (BC20NH14).At the molecular level, the singlet fission process involves a pairof neighboring molecules and is based on the coupling between an excitedsinglet state (S1S0) and two singlet-coupledtriplets ((T1T1)-T-1), which, typically,is influenced by an intermolecular charge transfer state. Taking datafrom periodic density functional theory and ab initio wave functioncalculations, we applied the non-orthogonal configuration interactionmethod to determine electronic coupling parameters. The comparisonof the results for both equilibrium structures reveal smaller SF couplingfor pentacene than for B,N-pentacene by a factor of & SIM;5. Introductionof the dynamic behavior to the crystals (vibrations, thermal motion)provides a more realistic picture of the effect of the disorder atthe molecular level on the SF efficiency. The coupling values associatedto out-of-equilibrium structures show that most of the S1S0/(T1T1)-T-1 couplings remainvirtually constant or slightly increase for pentacene when moleculardisorder is introduced. Homologous calculations on B,N-pentacene showa generalized decrease in the coupling values, notably if large phonondisplacements are considered. A few of the structures analyzed featuremuch larger SF coupling if some distortion results in (nearly) degeneratecharge transfer and excited singlet and triplet states. For theseparticular situations, an acceleration of the SF process could occuralthough in competition with electron-hole separation as analternative pathway.
Àrees temàtiques: Surfaces, coatings and films Química Physical and theoretical chemistry Nanoscience and nanotechnology Nanoscience & nanotechnology Medicina ii Medicina i Materials science, multidisciplinary Materiais Interdisciplinar General energy Farmacia Ensino Engenharias iv Engenharias iii Engenharias ii Engenharias i Energy (miscellaneous) Energy (all) Electronic, optical and magnetic materials Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Ciências ambientais Ciências agrárias i Chemistry, physical Biotecnología Biodiversidade Astronomia / física
Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
Adreça de correu electrònic de l'autor: coen.degraaf@urv.cat javier.lopez@urv.cat aitor.sanchezm@estudiants.urv.cat
Identificador de l'autor: 0000-0001-8114-6658 0000-0003-0322-6796
Data d'alta del registre: 2024-04-06
Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
Enllaç font original: https://pubs.acs.org/doi/10.1021/acs.jpcc.3c02083
URL Document de llicència: http://repositori.urv.cat/ca/proteccio-de-dades/
Referència a l'article segons font original: Journal Of Physical Chemistry c.
Referència de l'ítem segons les normes APA: López, X; Straatsma, TP; Sánchez-Mansilla, A; de Graaf, C (2023). Non-orthogonal Configuration Interaction Study on the Effect of Thermal Distortions on the Singlet Fission Process in Photoexcited Pure and B,N-Doped Pentacene Crystals. Journal Of Physical Chemistry c, (), -. DOI: 10.1021/acs.jpcc.3c02083
DOI de l'article: 10.1021/acs.jpcc.3c02083
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2023
Tipus de publicació: Journal Publications
Repositori URV