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Nonlocal STM Manipulation of Chlorobenzene on Si(111)-7 × 7: Potentials, Kinetics, and First-Principles Molecular Dynamics Calculations for Open Systems

Tina Gaebel, Daniel Bein, Daniel Mathauer, Manuel Utecht, Richard Palmer Orcid Logo, Tillmann Klamroth

The Journal of Physical Chemistry C, Volume: 125, Issue: 22, Pages: 12175 - 12184

Swansea University Author: Richard Palmer Orcid Logo

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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...

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Published in: The Journal of Physical Chemistry C
ISSN: 1932-7447 1932-7455
Published: American Chemical Society (ACS) 2021
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URI: https://cronfa.swan.ac.uk/Record/cronfa57238
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first_indexed 2021-06-29T09:23:35Z
last_indexed 2021-12-01T04:16:24Z
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spelling 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 11.037056

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