Journal article 463 views
Nonlocal STM Manipulation of Chlorobenzene on Si(111)-7 × 7: Potentials, Kinetics, and First-Principles Molecular Dynamics Calculations for Open Systems
The Journal of Physical Chemistry C, Volume: 125, Issue: 22, Pages: 12175 - 12184
Swansea University Author: Richard Palmer
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DOI (Published version): 10.1021/acs.jpcc.1c02612
Abstract
We use quantum chemical cluster models together with constrained density functional theory (DFT) and ab initio molecular dynamics (AIMD) for open system to simulate and rationalize nonlocal scanning tunneling microscope (STM) manipulation experiments for chlorobenzene (PhCl) on a Si(111)-7 × 7 surfa...
Published in: | The Journal of Physical Chemistry C |
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ISSN: | 1932-7447 1932-7455 |
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American Chemical Society (ACS)
2021
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URI: | https://cronfa.swan.ac.uk/Record/cronfa57238 |
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2021-11-30T16:05:59.0471962 v2 57238 2021-06-29 Nonlocal STM Manipulation of Chlorobenzene on Si(111)-7 × 7: Potentials, Kinetics, and First-Principles Molecular Dynamics Calculations for Open Systems 6ae369618efc7424d9774377536ea519 0000-0001-8728-8083 Richard Palmer Richard Palmer true false 2021-06-29 MECH We use quantum chemical cluster models together with constrained density functional theory (DFT) and ab initio molecular dynamics (AIMD) for open system to simulate and rationalize nonlocal scanning tunneling microscope (STM) manipulation experiments for chlorobenzene (PhCl) on a Si(111)-7 × 7 surface. We consider three different processes, namely, the electron-induced dissociation of the carbon–chlorine bond for physisorbed PhCl molecules at low temperatures and the electron- or hole-induced desorption of chemisorbed PhCl at 300 K. All processes can be induced nonlocally, i.e., up to several nanometers (nm) away from the injection site, in STM experiments. We rationalize and explain the experimental findings regarding the STM-induced dissociation using constrained DFT. The coupling of STM-induced ion resonances to nuclear degrees of freedom is simulated with AIMD using the Gadzuk averaging approach for open systems. From this data, we predict a 4 fs lifetime for the cationic resonance. For the anion model, desorption could not be observed. In addition, the same cluster models are used for transition-state theory calculations, which are compared to and validated against time-lapse STM experiments. Journal Article The Journal of Physical Chemistry C 125 22 12175 12184 American Chemical Society (ACS) 1932-7447 1932-7455 Adsorption, Resonance structures, Cluster chemistry, Potential energy, Molecules 10 6 2021 2021-06-10 10.1021/acs.jpcc.1c02612 COLLEGE NANME Mechanical Engineering COLLEGE CODE MECH Swansea University 2021-11-30T16:05:59.0471962 2021-06-29T10:19:35.8249915 Faculty of Science and Engineering School of Aerospace, Civil, Electrical, General and Mechanical Engineering - Mechanical Engineering Tina Gaebel 1 Daniel Bein 2 Daniel Mathauer 3 Manuel Utecht 4 Richard Palmer 0000-0001-8728-8083 5 Tillmann Klamroth 6 |
title |
Nonlocal STM Manipulation of Chlorobenzene on Si(111)-7 × 7: Potentials, Kinetics, and First-Principles Molecular Dynamics Calculations for Open Systems |
spellingShingle |
Nonlocal STM Manipulation of Chlorobenzene on Si(111)-7 × 7: Potentials, Kinetics, and First-Principles Molecular Dynamics Calculations for Open Systems Richard Palmer |
title_short |
Nonlocal STM Manipulation of Chlorobenzene on Si(111)-7 × 7: Potentials, Kinetics, and First-Principles Molecular Dynamics Calculations for Open Systems |
title_full |
Nonlocal STM Manipulation of Chlorobenzene on Si(111)-7 × 7: Potentials, Kinetics, and First-Principles Molecular Dynamics Calculations for Open Systems |
title_fullStr |
Nonlocal STM Manipulation of Chlorobenzene on Si(111)-7 × 7: Potentials, Kinetics, and First-Principles Molecular Dynamics Calculations for Open Systems |
title_full_unstemmed |
Nonlocal STM Manipulation of Chlorobenzene on Si(111)-7 × 7: Potentials, Kinetics, and First-Principles Molecular Dynamics Calculations for Open Systems |
title_sort |
Nonlocal STM Manipulation of Chlorobenzene on Si(111)-7 × 7: Potentials, Kinetics, and First-Principles Molecular Dynamics Calculations for Open Systems |
author_id_str_mv |
6ae369618efc7424d9774377536ea519 |
author_id_fullname_str_mv |
6ae369618efc7424d9774377536ea519_***_Richard Palmer |
author |
Richard Palmer |
author2 |
Tina Gaebel Daniel Bein Daniel Mathauer Manuel Utecht Richard Palmer Tillmann Klamroth |
format |
Journal article |
container_title |
The Journal of Physical Chemistry C |
container_volume |
125 |
container_issue |
22 |
container_start_page |
12175 |
publishDate |
2021 |
institution |
Swansea University |
issn |
1932-7447 1932-7455 |
doi_str_mv |
10.1021/acs.jpcc.1c02612 |
publisher |
American Chemical Society (ACS) |
college_str |
Faculty of Science and Engineering |
hierarchytype |
|
hierarchy_top_id |
facultyofscienceandengineering |
hierarchy_top_title |
Faculty of Science and Engineering |
hierarchy_parent_id |
facultyofscienceandengineering |
hierarchy_parent_title |
Faculty of Science and Engineering |
department_str |
School of Aerospace, Civil, Electrical, General and Mechanical Engineering - Mechanical Engineering{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Aerospace, Civil, Electrical, General and Mechanical Engineering - Mechanical Engineering |
document_store_str |
0 |
active_str |
0 |
description |
We use quantum chemical cluster models together with constrained density functional theory (DFT) and ab initio molecular dynamics (AIMD) for open system to simulate and rationalize nonlocal scanning tunneling microscope (STM) manipulation experiments for chlorobenzene (PhCl) on a Si(111)-7 × 7 surface. We consider three different processes, namely, the electron-induced dissociation of the carbon–chlorine bond for physisorbed PhCl molecules at low temperatures and the electron- or hole-induced desorption of chemisorbed PhCl at 300 K. All processes can be induced nonlocally, i.e., up to several nanometers (nm) away from the injection site, in STM experiments. We rationalize and explain the experimental findings regarding the STM-induced dissociation using constrained DFT. The coupling of STM-induced ion resonances to nuclear degrees of freedom is simulated with AIMD using the Gadzuk averaging approach for open systems. From this data, we predict a 4 fs lifetime for the cationic resonance. For the anion model, desorption could not be observed. In addition, the same cluster models are used for transition-state theory calculations, which are compared to and validated against time-lapse STM experiments. |
published_date |
2021-06-10T04:12:49Z |
_version_ |
1763753873286103040 |
score |
11.029746 |