Articolo in rivista, 2021, ENG, 10.1021/acs.jpcc.0c08815
Sementa L.; Monti M.; Toffoli D.; Posada-Amarillas A.; Stener M.; Fortunelli A.
CNR-ICCOM and IPCF, Consiglio Nazionale Delle Ricerche, ThC2-Lab and Molecular Modelling Team, Pisa, 56124, Italy; Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Trieste, Trieste, I-34127, Italy; Departamento de Investigación en Física, Universidad de Sonora, Hermosillo, Sonora, 83000, Mexico
We report a computational study and analysis of the optical absorption and photodecay processes in two subnanometer metal complexes deposited on an oxide support, the regular MgO(100) surface: (i) Ag3(HCO3)(C2H4)2(O) and (ii) Ag3(CO2F)(C2H4)2(O). These aggregates are chosen as derivatives of a Ag3(CO3)(C2H4)2(O) ligand/metal-cluster/support complex, previously singled out as a key intermediate in the path of ethylene partial oxidation to ethylene epoxide catalyzed by Ag3/MgO(100), and serve as model systems to investigate photochemical phenomena in ligand/metal-cluster/support complexes by subnanometer metal catalysts, an appealing field for future research. After generating optimized initial configurations and building cluster models that take properly into account the effect of the charge-separated oxide support, we use time-dependent density-functional theory (TDDFT) to determine first the photoabsorption spectra of the two aggregates and then to follow the evolution of their excited states in the optical region. We show that complexes containing such bicarbonate and fluorocarbonate groups are sensitive to optical adsorption, often leading to ligand detachment and/or cluster disaggregation, thus pointing to an "optical frailty"of these subnanometer cluster species, possibly rationalizing previous experimental observations. Additionally, we correlate the nature of the given excitations and of the corresponding photoinduced reaction products via an analysis of overlap population-density of states (OP-DOS), geometric parameters, and spatial distribution of the molecular orbitals involved in the excitation, thus providing the set of methodological tools needed to explore this novel field.
Journal of physical chemistry. C 125 (3), pp. 2022–2032
computational studies, optical absorption, photodecay processes, subnanometer metal complexes, oxide support
Fortunelli Alessandro, Sementa Luca
ICCOM – Istituto di chimica dei composti organo metallici, IPCF – Istituto per i processi chimico-fisici
ID: 444330
Year: 2021
Type: Articolo in rivista
Creation: 2021-02-05 14:11:53.000
Last update: 2022-10-04 10:43:07.000
CNR authors
External links
OAI-PMH: Dublin Core
OAI-PMH: Mods
OAI-PMH: RDF
URL: http://www.scopus.com/inward/record.url?eid=2-s2.0-85100007589&partnerID=q2rCbXpz
External IDs
CNR OAI-PMH: oai:it.cnr:prodotti:444330
DOI: 10.1021/acs.jpcc.0c08815
Scopus: 2-s2.0-85100007589