Cargando...
Fecha
2022-08-18
Derechos de acceso
info:eu-repo/semantics/openAccess
Título de la revista
ISSN de la revista
Título del volumen
Editorial
American Institute of Physics
Citas
Resumen
In this work, we have studied, within density functional theory, the interaction of NO with pure and oxidized silver clusters, both anionic and cationic, composed from 11 to 13 Ag atoms. In that size interval, shell closing effects are not expected, and structural and electronic odd–even effects will determine the strength of interaction. First, we obtained that species Ag±n and AgnO± with odd number of electrons (n = 12) adsorb NO with higher energy than their neighbors (n = 11 and 13). This result is in agreement with the facts observed in recent mass spectroscopy measurements, which were performed, however, at finite temperature. The adsorption energy is about twice for oxidized clusters compared to pure ones and higher for anions than for cations. Second, the adsorption of another NO molecule on AgnNO± forms Agn(NO)±2 , with the dimer (NO)2 in cis configuration, and binding the two N atoms with two neighbor Ag atoms. The n = 12 species show the higher adsorption energy again. Third, in the absence of reaction barriers, all complexes Agn(NO)±2 dissociate spontaneously into AgnO± and N2O, except the n = 12 anion. The maximum high barrier along the dissociation path of Ag13(NO)−2 is about 0.7 eV. Further analysis of projected density of states for Ag11−13(NO)±x (x = 0, 1, 2) molecules shows that bonding between NO and Ag clusters mainly occurs in the energy range between −3.0 and 3.0 eV. The overlap between 4d of Ag and 2p of N and O is larger for Ag12(NO)±2 than for neighbor sizes. For n = 12, the d bands are close to the (NO)2 2π orbital, leading to extra back-donation charge from the 4d of Ag to the closer 2π orbital of (NO)2.
Descripción
The registered version of this article, first published in The Journal of Chemical Physics 157, 074310 (2022), is available online at the publisher's website: https://doi.org/10.1063/5.0094996
La versión registrada de este artículo, publicado por primera vez en The Journal of Chemical Physics 157, 074310 (2022), está disponible en línea en el sitio web del editor: https://doi.org/10.1063/5.0094996
La versión registrada de este artículo, publicado por primera vez en The Journal of Chemical Physics 157, 074310 (2022), está disponible en línea en el sitio web del editor: https://doi.org/10.1063/5.0094996
Categorías UNESCO
Palabras clave
Citación
Fernández, E. M., & Balbás, L. C. (2022). Interactions of nitric oxide molecules with pure and oxidized silver clusters Agn±/AgnO± (n=11-13): A computational study. The Journal of chemical physics, 157(7), 74310. https://doi.org/10.1063/5.0094996
Centro
Facultad de Ciencias
Departamento
Física Fundamental