Optical Activity of Metal Nanoclusters Deposited on Regular and Doped Oxide Supports from First-Principles Simulations

We report a computational study and analysis of the optical absorption processes of Ag20 and Au20 clusters deposited on the magnesium oxide (100) facet, both regular and including point defects. Ag20 and Au20...

Descripción completa

Guardado en:

Detalles Bibliográficos
Autores principales:	Luca Sementa, Mauro Stener, Alessandro Fortunelli
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	metal clusters optical photo-absorption Time-Dependent Density-Functional Theory (TDDFT) cluster/oxide interface first-principles modeling photo-enhanced processes Organic chemistry QD241-441
Acceso en línea:	https://doaj.org/article/f6c4bd4dd3004ef6a2d1ba666b4afda6
Etiquetas:	Agregar Etiqueta Sin Etiquetas, Sea el primero en etiquetar este registro!

id	oai:doaj.org-article:f6c4bd4dd3004ef6a2d1ba666b4afda6
record_format	dspace
spelling	oai:doaj.org-article:f6c4bd4dd3004ef6a2d1ba666b4afda62021-11-25T18:28:44ZOptical Activity of Metal Nanoclusters Deposited on Regular and Doped Oxide Supports from First-Principles Simulations10.3390/molecules262269611420-3049https://doaj.org/article/f6c4bd4dd3004ef6a2d1ba666b4afda62021-11-01T00:00:00Zhttps://www.mdpi.com/1420-3049/26/22/6961https://doaj.org/toc/1420-3049We report a computational study and analysis of the optical absorption processes of Ag<sub>20</sub> and Au<sub>20</sub> clusters deposited on the magnesium oxide (100) facet, both regular and including point defects. Ag<sub>20</sub> and Au<sub>20</sub> are taken as models of metal nanoparticles and their plasmonic response, MgO as a model of a simple oxide support. We consider oxide defects both on the oxygen anion framework (i.e., a neutral oxygen vacancy) and in the magnesium cation framework (i.e., replacing Mg<sup>++</sup> with a transition metal: Cu<sup>++</sup> or Co<sup>++</sup>). We relax the clusters’ geometries via Density-Functional Theory (DFT) and calculate the photo-absorption spectra via Time-Dependent DFT (TDDFT) simulations on the relaxed geometries. We find that the substrate/cluster interaction induces a broadening and a red-shift of the excited states of the clusters, phenomena that are enhanced by the presence of an oxygen vacancy and its localized excitations. The presence of a transition-metal dopant does not qualitatively affect the spectral profile. However, when it lies next to an oxygen vacancy for Ag<sub>20</sub>, it can strongly enhance the component of the cluster excitations perpendicular to the surface, thus favoring charge injection.Luca SementaMauro StenerAlessandro FortunelliMDPI AGarticlemetal clustersoptical photo-absorptionTime-Dependent Density-Functional Theory (TDDFT)cluster/oxide interfacefirst-principles modelingphoto-enhanced processesOrganic chemistryQD241-441ENMolecules, Vol 26, Iss 6961, p 6961 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	metal clusters optical photo-absorption Time-Dependent Density-Functional Theory (TDDFT) cluster/oxide interface first-principles modeling photo-enhanced processes Organic chemistry QD241-441
spellingShingle	metal clusters optical photo-absorption Time-Dependent Density-Functional Theory (TDDFT) cluster/oxide interface first-principles modeling photo-enhanced processes Organic chemistry QD241-441 Luca Sementa Mauro Stener Alessandro Fortunelli Optical Activity of Metal Nanoclusters Deposited on Regular and Doped Oxide Supports from First-Principles Simulations
description	We report a computational study and analysis of the optical absorption processes of Ag<sub>20</sub> and Au<sub>20</sub> clusters deposited on the magnesium oxide (100) facet, both regular and including point defects. Ag<sub>20</sub> and Au<sub>20</sub> are taken as models of metal nanoparticles and their plasmonic response, MgO as a model of a simple oxide support. We consider oxide defects both on the oxygen anion framework (i.e., a neutral oxygen vacancy) and in the magnesium cation framework (i.e., replacing Mg<sup>++</sup> with a transition metal: Cu<sup>++</sup> or Co<sup>++</sup>). We relax the clusters’ geometries via Density-Functional Theory (DFT) and calculate the photo-absorption spectra via Time-Dependent DFT (TDDFT) simulations on the relaxed geometries. We find that the substrate/cluster interaction induces a broadening and a red-shift of the excited states of the clusters, phenomena that are enhanced by the presence of an oxygen vacancy and its localized excitations. The presence of a transition-metal dopant does not qualitatively affect the spectral profile. However, when it lies next to an oxygen vacancy for Ag<sub>20</sub>, it can strongly enhance the component of the cluster excitations perpendicular to the surface, thus favoring charge injection.
format	article
author	Luca Sementa Mauro Stener Alessandro Fortunelli
author_facet	Luca Sementa Mauro Stener Alessandro Fortunelli
author_sort	Luca Sementa
title	Optical Activity of Metal Nanoclusters Deposited on Regular and Doped Oxide Supports from First-Principles Simulations
title_short	Optical Activity of Metal Nanoclusters Deposited on Regular and Doped Oxide Supports from First-Principles Simulations
title_full	Optical Activity of Metal Nanoclusters Deposited on Regular and Doped Oxide Supports from First-Principles Simulations
title_fullStr	Optical Activity of Metal Nanoclusters Deposited on Regular and Doped Oxide Supports from First-Principles Simulations
title_full_unstemmed	Optical Activity of Metal Nanoclusters Deposited on Regular and Doped Oxide Supports from First-Principles Simulations
title_sort	optical activity of metal nanoclusters deposited on regular and doped oxide supports from first-principles simulations
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/f6c4bd4dd3004ef6a2d1ba666b4afda6
work_keys_str_mv	AT lucasementa opticalactivityofmetalnanoclustersdepositedonregularanddopedoxidesupportsfromfirstprinciplessimulations AT maurostener opticalactivityofmetalnanoclustersdepositedonregularanddopedoxidesupportsfromfirstprinciplessimulations AT alessandrofortunelli opticalactivityofmetalnanoclustersdepositedonregularanddopedoxidesupportsfromfirstprinciplessimulations
_version_	1718411112580382720

Optical Activity of Metal Nanoclusters Deposited on Regular and Doped Oxide Supports from First-Principles Simulations

Ejemplares similares