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Thermodynamic driving forces for substrate atom extraction by adsorption of strong electron acceptor molecules
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Ryan, Paul, Blowey, Philip James, Sohail, Billal S., Rochford, Luke A., Duncan, David A., Lee, Tien-Lin, Starrs, Peter, Costantini, Giovanni, Maurer, Reinhard J. and Woodruff, David Phillip (2022) Thermodynamic driving forces for substrate atom extraction by adsorption of strong electron acceptor molecules. The Journal of Physical Chemistry C, 126 (13). pp. 6082-6090. doi:10.1021/acs.jpcc.2c00711 ISSN 1932-7447.
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Official URL: http://dx.doi.org/10.1021/acs.jpcc.2c00711
Abstract
A quantitative structural investigation is reported, aimed at resolving the issue of whether substrate adatoms are incorporated into the monolayers formed by strong molecular electron acceptors deposited onto metallic electrodes. A combination of normal-incidence X-ray standing waves, low-energy electron diffraction, scanning tunnelling microscopy, and X-ray photoelectron spectroscopy measurements demonstrate that the systems TCNQ and F4TCNQ on Ag(100) lie at the boundary between these two possibilities and thus represent ideal model systems with which to study this effect. A room-temperature commensurate phase of adsorbed TCNQ is found not to involve Ag adatoms, but to adopt an inverted bowl configuration, long predicted but not previously identified experimentally. By contrast, a similar phase of adsorbed F4TCNQ does lead to Ag adatom incorporation in the overlayer, the cyano end groups of the molecule being twisted relative to the planar quinoid ring. Density functional theory (DFT) calculations show that this behavior is consistent with the adsorption energetics. Annealing of the commensurate TCNQ overlayer phase leads to an incommensurate phase that does appear to incorporate Ag adatoms. Our results indicate that the inclusion (or exclusion) of metal atoms into the organic monolayers is the result of both thermodynamic and kinetic factors.
| Item Type: | Journal Article | |||||||||||||||||||||
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| Subjects: | Q Science > QC Physics Q Science > QD Chemistry |
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| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry Faculty of Science, Engineering and Medicine > Science > Physics Faculty of Science, Engineering and Medicine > Science > Chemistry > Computational and Theoretical Chemistry Centre |
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| Library of Congress Subject Headings (LCSH): | Surfaces (Physics), Density functionals , Organic semiconductors, Interfaces (Physical sciences), Adsorption | |||||||||||||||||||||
| Journal or Publication Title: | The Journal of Physical Chemistry C | |||||||||||||||||||||
| Publisher: | American Chemical Society | |||||||||||||||||||||
| ISSN: | 1932-7447 | |||||||||||||||||||||
| Official Date: | 7 April 2022 | |||||||||||||||||||||
| Dates: |
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| Volume: | 126 | |||||||||||||||||||||
| Number: | 13 | |||||||||||||||||||||
| Page Range: | pp. 6082-6090 | |||||||||||||||||||||
| DOI: | 10.1021/acs.jpcc.2c00711 | |||||||||||||||||||||
| Status: | Peer Reviewed | |||||||||||||||||||||
| Publication Status: | Published | |||||||||||||||||||||
| Access rights to Published version: | Open Access (Creative Commons) | |||||||||||||||||||||
| Date of first compliant deposit: | 4 April 2022 | |||||||||||||||||||||
| Date of first compliant Open Access: | 20 April 2022 | |||||||||||||||||||||
| RIOXX Funder/Project Grant: |
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