Autor según el artículo: Saureu, Sergi; de Graaf, Coen;
Departamento: Química Física i Inorgànica
Autor/es de la URV: De Graaf, Cornelis
Palabras clave: Transition-metal complexes Transition Temperature State energetics Spectroscopy Iron(iii) compounds Inorganic chemistry Fe(phen)(2)(ncs)(2) Electronic-structure Electronic structure Dynamics Basis-sets 2nd-order perturbation-theory
Resumen: Two light-induced spin-crossover Fe(III) compounds have been studied with time-dependent density functional theory (TD-DFT) to investigate the deactivation mechanism and the role of the ligand-field states as intermediates in this process. The B3LYP* functional has previously shown its ability to accurately describe (light-induced) spin-crossover in Fe(II) complexes. Here, we establish its performance for Fe(III) systems using [Fe(qsal)2]+ (Hqsal = 2-[(8-quinolinylimino)methyl]phenol) and [Fe(pap)2]+ (Hpap = 2-(2-pyridylmethyleneamino)phenol) as test cases comparing the B3LYP* results to experimental information and to multiconfigurational wave function results. In addition to rather accurate high spin (HS) and low spin (LS) state geometries, B3LYP* also predicts ligand-to-metal charge transfer (LMCT) states with large oscillator strength in the energy range where the UV-VIS spectrum shows an intense absorption band, whereas optically allowed π-π* excitations on the ligands were calculated at higher energy. Subsequently, we have generated a two-dimensional potential energy surface of the HS and LS states varying the Fe-N and Fe-O distances. LMCT and metal centered (MC) excited states were followed along the approximate minimal energy path that connects the minima of the HS and LS on this surface. The 2LMCT state has a minimum in the same region as the initial LS state, where we also observe a crossing with the intermediate spin (IS) state. Upon the expansion of the coordination sphere of the Fe(III) ion, the IS state crosses with the HS state and further expansion of the coordination sphere leads to the excited spin state trapping as observed in experiment. The calculation of the intersystem crossing rates reveals that the deactivation from 2LMCT → IS → HS competes with the 2LMCT → IS → LS pathway, in line with the low efficiency encountered in experiments.
Áreas temáticas: Química Physics, atomic, molecular & chemical Physics and astronomy (miscellaneous) Physics and astronomy (all) Physical and theoretical chemistry Odontología Medicina ii Medicina i Materiais Matemática / probabilidade e estatística Interdisciplinar Geociências General physics and astronomy General medicine Farmacia Ensino Engenharias iv Engenharias iii Engenharias ii Ciências biológicas ii Ciências biológicas i Ciências ambientais Ciências agrárias i Ciência de alimentos Ciência da computação Chemistry, physical Biotecnología Biodiversidade Astronomia / física
Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
Direcció de correo del autor: coen.degraaf@urv.cat
Identificador del autor: 0000-0001-8114-6658
Fecha de alta del registro: 2024-09-07
Versión del articulo depositado: info:eu-repo/semantics/submittedVersion
URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
Referencia al articulo segun fuente origial: Physical Chemistry Chemical Physics. 18 (2): 1233-1244
Referencia de l'ítem segons les normes APA: Saureu, Sergi; de Graaf, Coen; (2016). TD-DFT study of the light-induced spin crossover of Fe(III) complexes. Physical Chemistry Chemical Physics, 18(2), 1233-1244. DOI: 10.1039/c5cp06620d
Entidad: Universitat Rovira i Virgili
Año de publicación de la revista: 2016
Tipo de publicación: Journal Publications
Repositori URV