Benzene and Pyridine on Silicon (001): A Trial Ground for Long-Range Corrections in Density Functional Theory

The adsorption chemistry of benzene and pyridine on the silicon (001) surface is characterized by two prominent adsorbate configurations: a precursor structure bonded to a single Si–Si dimer and a “tight-bridge” configuration that connects two adjacent dimers. We examine here the performance of 20 d...

Full description

Bibliographic Details
Main Authors: Warschkow, O., Bennett, J., Miwa, J., Lopinski, G., Rosei, F., McKenzie, D., Marks, Nigel
Format: Journal Article
Published: American Chemical Society 2017
Online Access:http://hdl.handle.net/20.500.11937/54932
_version_ 1848759500993986560
author Warschkow, O.
Bennett, J.
Miwa, J.
Lopinski, G.
Rosei, F.
McKenzie, D.
Marks, Nigel
author_facet Warschkow, O.
Bennett, J.
Miwa, J.
Lopinski, G.
Rosei, F.
McKenzie, D.
Marks, Nigel
author_sort Warschkow, O.
building Curtin Institutional Repository
collection Online Access
description The adsorption chemistry of benzene and pyridine on the silicon (001) surface is characterized by two prominent adsorbate configurations: a precursor structure bonded to a single Si–Si dimer and a “tight-bridge” configuration that connects two adjacent dimers. We examine here the performance of 20 density functionals in predicting the relative stability of these two configurations. Discrepancies between the predicted and experimentally observed preferred structures highlight the importance of long-range exact-exchange terms in these adsorbate systems. These terms, however, tend to be detrimental to the prediction of adsorption and activation energies. We discuss this conundrum in terms of systematic exchange-correlation errors that scale with the number of molecule–surface bonds.
first_indexed 2025-11-14T10:00:53Z
format Journal Article
id curtin-20.500.11937-54932
institution Curtin University Malaysia
institution_category Local University
last_indexed 2025-11-14T10:00:53Z
publishDate 2017
publisher American Chemical Society
recordtype eprints
repository_type Digital Repository
spelling curtin-20.500.11937-549322017-11-03T00:21:33Z Benzene and Pyridine on Silicon (001): A Trial Ground for Long-Range Corrections in Density Functional Theory Warschkow, O. Bennett, J. Miwa, J. Lopinski, G. Rosei, F. McKenzie, D. Marks, Nigel The adsorption chemistry of benzene and pyridine on the silicon (001) surface is characterized by two prominent adsorbate configurations: a precursor structure bonded to a single Si–Si dimer and a “tight-bridge” configuration that connects two adjacent dimers. We examine here the performance of 20 density functionals in predicting the relative stability of these two configurations. Discrepancies between the predicted and experimentally observed preferred structures highlight the importance of long-range exact-exchange terms in these adsorbate systems. These terms, however, tend to be detrimental to the prediction of adsorption and activation energies. We discuss this conundrum in terms of systematic exchange-correlation errors that scale with the number of molecule–surface bonds. 2017 Journal Article http://hdl.handle.net/20.500.11937/54932 10.1021/acs.jpcc.7b03618 American Chemical Society restricted
spellingShingle Warschkow, O.
Bennett, J.
Miwa, J.
Lopinski, G.
Rosei, F.
McKenzie, D.
Marks, Nigel
Benzene and Pyridine on Silicon (001): A Trial Ground for Long-Range Corrections in Density Functional Theory
title Benzene and Pyridine on Silicon (001): A Trial Ground for Long-Range Corrections in Density Functional Theory
title_full Benzene and Pyridine on Silicon (001): A Trial Ground for Long-Range Corrections in Density Functional Theory
title_fullStr Benzene and Pyridine on Silicon (001): A Trial Ground for Long-Range Corrections in Density Functional Theory
title_full_unstemmed Benzene and Pyridine on Silicon (001): A Trial Ground for Long-Range Corrections in Density Functional Theory
title_short Benzene and Pyridine on Silicon (001): A Trial Ground for Long-Range Corrections in Density Functional Theory
title_sort benzene and pyridine on silicon (001): a trial ground for long-range corrections in density functional theory
url http://hdl.handle.net/20.500.11937/54932