Cargando…
A Comprehensive Study of the Bridge Site and Substrate Relaxation Asymmetry for Methanethiol Adsorption on Au(111) at Low Coverage
[Image: see text] We use dispersion-corrected density functional theory to explore the bridge-site asymmetry for methanethiol adsorbed on Au(111) with two different S–C bond orientations. We attribute the asymmetry to the intrinsic character of the Au(111) surface rather than the adsorbate. The pref...
Autores principales: | , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2020
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7450628/ https://www.ncbi.nlm.nih.gov/pubmed/32875222 http://dx.doi.org/10.1021/acsomega.0c02328 |
_version_ | 1783574841904857088 |
---|---|
author | Bhattacharya, Soumya Speyer, Gil Ferry, David K. Bumm, Lloyd A. |
author_facet | Bhattacharya, Soumya Speyer, Gil Ferry, David K. Bumm, Lloyd A. |
author_sort | Bhattacharya, Soumya |
collection | PubMed |
description | [Image: see text] We use dispersion-corrected density functional theory to explore the bridge-site asymmetry for methanethiol adsorbed on Au(111) with two different S–C bond orientations. We attribute the asymmetry to the intrinsic character of the Au(111) surface rather than the adsorbate. The preference for bridge-fcc versus bridge-hcp SCH(3) adsorption sites is controlled by the S–C bond orientation. The system energy difference favors the bridge-fcc site by 8.1 meV on the unrelaxed Au(111) surface. Relaxing the Au substrate increased this energy difference to 26.1 meV. This asymmetry is also reflected in the atomic displacement of the relaxed Au surface. Although in both cases, the bridge-site Au atoms shift away from the fcc 3-fold hollow site, the motion is greater for the bridge-fcc allowing a more favorable geometry for the sulfur atom to bond to the bridging atoms. We confirm that the adsorption energy is strongly dependent on the S–C bond orientation and position, which can be understood in terms of a simple coordination geometry model. This work has important implications for alkanethiol surface diffusion and the structure of their self-assembled monolayers. |
format | Online Article Text |
id | pubmed-7450628 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-74506282020-08-31 A Comprehensive Study of the Bridge Site and Substrate Relaxation Asymmetry for Methanethiol Adsorption on Au(111) at Low Coverage Bhattacharya, Soumya Speyer, Gil Ferry, David K. Bumm, Lloyd A. ACS Omega [Image: see text] We use dispersion-corrected density functional theory to explore the bridge-site asymmetry for methanethiol adsorbed on Au(111) with two different S–C bond orientations. We attribute the asymmetry to the intrinsic character of the Au(111) surface rather than the adsorbate. The preference for bridge-fcc versus bridge-hcp SCH(3) adsorption sites is controlled by the S–C bond orientation. The system energy difference favors the bridge-fcc site by 8.1 meV on the unrelaxed Au(111) surface. Relaxing the Au substrate increased this energy difference to 26.1 meV. This asymmetry is also reflected in the atomic displacement of the relaxed Au surface. Although in both cases, the bridge-site Au atoms shift away from the fcc 3-fold hollow site, the motion is greater for the bridge-fcc allowing a more favorable geometry for the sulfur atom to bond to the bridging atoms. We confirm that the adsorption energy is strongly dependent on the S–C bond orientation and position, which can be understood in terms of a simple coordination geometry model. This work has important implications for alkanethiol surface diffusion and the structure of their self-assembled monolayers. American Chemical Society 2020-08-13 /pmc/articles/PMC7450628/ /pubmed/32875222 http://dx.doi.org/10.1021/acsomega.0c02328 Text en Copyright © 2020 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes. |
spellingShingle | Bhattacharya, Soumya Speyer, Gil Ferry, David K. Bumm, Lloyd A. A Comprehensive Study of the Bridge Site and Substrate Relaxation Asymmetry for Methanethiol Adsorption on Au(111) at Low Coverage |
title | A Comprehensive Study of the
Bridge Site and Substrate
Relaxation Asymmetry for Methanethiol Adsorption on Au(111) at Low
Coverage |
title_full | A Comprehensive Study of the
Bridge Site and Substrate
Relaxation Asymmetry for Methanethiol Adsorption on Au(111) at Low
Coverage |
title_fullStr | A Comprehensive Study of the
Bridge Site and Substrate
Relaxation Asymmetry for Methanethiol Adsorption on Au(111) at Low
Coverage |
title_full_unstemmed | A Comprehensive Study of the
Bridge Site and Substrate
Relaxation Asymmetry for Methanethiol Adsorption on Au(111) at Low
Coverage |
title_short | A Comprehensive Study of the
Bridge Site and Substrate
Relaxation Asymmetry for Methanethiol Adsorption on Au(111) at Low
Coverage |
title_sort | comprehensive study of the
bridge site and substrate
relaxation asymmetry for methanethiol adsorption on au(111) at low
coverage |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7450628/ https://www.ncbi.nlm.nih.gov/pubmed/32875222 http://dx.doi.org/10.1021/acsomega.0c02328 |
work_keys_str_mv | AT bhattacharyasoumya acomprehensivestudyofthebridgesiteandsubstraterelaxationasymmetryformethanethioladsorptiononau111atlowcoverage AT speyergil acomprehensivestudyofthebridgesiteandsubstraterelaxationasymmetryformethanethioladsorptiononau111atlowcoverage AT ferrydavidk acomprehensivestudyofthebridgesiteandsubstraterelaxationasymmetryformethanethioladsorptiononau111atlowcoverage AT bummlloyda acomprehensivestudyofthebridgesiteandsubstraterelaxationasymmetryformethanethioladsorptiononau111atlowcoverage AT bhattacharyasoumya comprehensivestudyofthebridgesiteandsubstraterelaxationasymmetryformethanethioladsorptiononau111atlowcoverage AT speyergil comprehensivestudyofthebridgesiteandsubstraterelaxationasymmetryformethanethioladsorptiononau111atlowcoverage AT ferrydavidk comprehensivestudyofthebridgesiteandsubstraterelaxationasymmetryformethanethioladsorptiononau111atlowcoverage AT bummlloyda comprehensivestudyofthebridgesiteandsubstraterelaxationasymmetryformethanethioladsorptiononau111atlowcoverage |