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Unraveling the Planar-Globular Transition in Gold Nanoclusters through Evolutionary Search

Au nanoclusters are of technological relevance for catalysis, photonics, sensors, and of fundamental scientific interest owing to planar to globular structural transformation at an anomalously high number of atoms i.e. in the range 12–14. The nature and causes of this transition remain a mystery. In...

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Autores principales: Kinaci, Alper, Narayanan, Badri, Sen, Fatih G., Davis, Michael J., Gray, Stephen K., Sankaranarayanan, Subramanian K. R. S., Chan, Maria K. Y.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group 2016
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5124999/
https://www.ncbi.nlm.nih.gov/pubmed/27892462
http://dx.doi.org/10.1038/srep34974
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author Kinaci, Alper
Narayanan, Badri
Sen, Fatih G.
Davis, Michael J.
Gray, Stephen K.
Sankaranarayanan, Subramanian K. R. S.
Chan, Maria K. Y.
author_facet Kinaci, Alper
Narayanan, Badri
Sen, Fatih G.
Davis, Michael J.
Gray, Stephen K.
Sankaranarayanan, Subramanian K. R. S.
Chan, Maria K. Y.
author_sort Kinaci, Alper
collection PubMed
description Au nanoclusters are of technological relevance for catalysis, photonics, sensors, and of fundamental scientific interest owing to planar to globular structural transformation at an anomalously high number of atoms i.e. in the range 12–14. The nature and causes of this transition remain a mystery. In order to unravel this conundrum, high throughput density functional theory (DFT) calculations, coupled with a global structural optimization scheme based on a modified genetic algorithm (GA) are conducted. More than 20,000 Au(12), Au(13), and Au(14) nanoclusters are evaluated. With any DFT functional, globular and planar structures coexist across the size range of interest. The planar-globular transition is gradual at room temperature rather than a sharp transition as previously believed. The effects of anionicity, s-d band hybridization and long range interactions on the dimensional transition are quantified by using the structures adjacent to the minima. Anionicity marginally changes the relative stability of the clusters. The degree of s-d hybridization is varied via changing the Hubbard U value which corroborate that s-d hybridization alone does not stabilize planar structures. van der Waals interactions, on the other hand, stabilize globular structures. These results elucidate the balance between the different reasons of the dimensional transition in gold nanoclusters.
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spelling pubmed-51249992016-12-08 Unraveling the Planar-Globular Transition in Gold Nanoclusters through Evolutionary Search Kinaci, Alper Narayanan, Badri Sen, Fatih G. Davis, Michael J. Gray, Stephen K. Sankaranarayanan, Subramanian K. R. S. Chan, Maria K. Y. Sci Rep Article Au nanoclusters are of technological relevance for catalysis, photonics, sensors, and of fundamental scientific interest owing to planar to globular structural transformation at an anomalously high number of atoms i.e. in the range 12–14. The nature and causes of this transition remain a mystery. In order to unravel this conundrum, high throughput density functional theory (DFT) calculations, coupled with a global structural optimization scheme based on a modified genetic algorithm (GA) are conducted. More than 20,000 Au(12), Au(13), and Au(14) nanoclusters are evaluated. With any DFT functional, globular and planar structures coexist across the size range of interest. The planar-globular transition is gradual at room temperature rather than a sharp transition as previously believed. The effects of anionicity, s-d band hybridization and long range interactions on the dimensional transition are quantified by using the structures adjacent to the minima. Anionicity marginally changes the relative stability of the clusters. The degree of s-d hybridization is varied via changing the Hubbard U value which corroborate that s-d hybridization alone does not stabilize planar structures. van der Waals interactions, on the other hand, stabilize globular structures. These results elucidate the balance between the different reasons of the dimensional transition in gold nanoclusters. Nature Publishing Group 2016-11-28 /pmc/articles/PMC5124999/ /pubmed/27892462 http://dx.doi.org/10.1038/srep34974 Text en Copyright © 2016, The Author(s) http://creativecommons.org/licenses/by/4.0/ This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/
spellingShingle Article
Kinaci, Alper
Narayanan, Badri
Sen, Fatih G.
Davis, Michael J.
Gray, Stephen K.
Sankaranarayanan, Subramanian K. R. S.
Chan, Maria K. Y.
Unraveling the Planar-Globular Transition in Gold Nanoclusters through Evolutionary Search
title Unraveling the Planar-Globular Transition in Gold Nanoclusters through Evolutionary Search
title_full Unraveling the Planar-Globular Transition in Gold Nanoclusters through Evolutionary Search
title_fullStr Unraveling the Planar-Globular Transition in Gold Nanoclusters through Evolutionary Search
title_full_unstemmed Unraveling the Planar-Globular Transition in Gold Nanoclusters through Evolutionary Search
title_short Unraveling the Planar-Globular Transition in Gold Nanoclusters through Evolutionary Search
title_sort unraveling the planar-globular transition in gold nanoclusters through evolutionary search
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5124999/
https://www.ncbi.nlm.nih.gov/pubmed/27892462
http://dx.doi.org/10.1038/srep34974
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