Donor-Acceptor Co-Adsorption Ratio Controls the Structure and Electronic Properties of Two-Dimensional Alkali-Organic Networks on Ag(100)

B. Sohail; P. J. Blowey; L. A. Rochford; P. T.P. Ryan; D. A. Duncan; T. L. Lee; P. Starrs; G. Costantini; D. P. Woodruff; R. J. Maurer

doi:10.1021/acs.jpcc.2c08688

Donor-Acceptor Co-Adsorption Ratio Controls the Structure and Electronic Properties of Two-Dimensional Alkali-Organic Networks on Ag(100)

B. Sohail, P. J. Blowey, L. A. Rochford, P. T.P. Ryan, D. A. Duncan, T. L. Lee, P. Starrs, G. Costantini, D. P. Woodruff^*, R. J. Maurer^*

^*Corresponding author for this work

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Abstract

The results are presented of a detailed combined experimental and theoretical investigation of the influence of coadsorbed electron-donating alkali atoms and the prototypical electron acceptor molecule 7,7,8,8-tetracyanoquinodimethane (TCNQ) on the Ag(100) surface. Several coadsorption phases were characterized by scanning tunneling microscopy, low-energy electron diffraction, and soft X-ray photoelectron spectroscopy. Quantitative structural data were obtained using normal-incidence X-ray standing wave (NIXSW) measurements and compared with the results of density functional theory (DFT) calculations using several different methods of dispersion correction. Generally, good agreement between theory and experiment was achieved for the quantitative structures, albeit with the prediction of the alkali atom heights being challenging for some methods. The adsorption structures depend sensitively on the interplay of molecule-metal charge transfer and long-range dispersion forces, which are controlled by the composition ratio between alkali atoms and TCNQ. The large difference in atomic size between K and Cs has negligible effects on stability, whereas increasing the ratio of K/TCNQ from 1:4 to 1:1 leads to a weakening of molecule-metal interaction strength in favor of stronger ionic bonds within the two-dimensional alkali-organic network. A strong dependence of the work function on the alkali donor-TCNQ acceptor coadsorption ratio is predicted.

Original language	English
Pages (from-to)	2716-2727
Number of pages	12
Journal	Journal of Physical Chemistry C
Volume	127
Issue number	5
Early online date	26 Jan 2023
DOIs	https://doi.org/10.1021/acs.jpcc.2c08688
Publication status	Published - 9 Feb 2023

Bibliographical note

Funding Information:
The authors thank Diamond Light Source for allocations SI17261 and SI20785 of beam time at beamline I09 that contributed to the results presented here. P.T.P.R. and P.J.B. acknowledge financial support from Diamond Light Source and EPSRC. G.C. acknowledges financial support from the EU through the ERC Grant “VISUAL-MS” (Project ID: 308115). B.S. and R.J.M. acknowledge doctoral studentship funding from the EPSRC and the National Productivity Investment Fund (NPIF). R.J.M. acknowledges financial support via a UKRI Future Leaders Fellowship (MR/S016023/1). The authors acknowledge computing resources provided by the EPSRC-funded HPC Midlands+ Computing Centre (EP/P020232/1 and EP/T022108/1) and the EPSRC-funded Materials Chemistry Consortium (EP/R029431/1) for the ARCHER2 U.K. National Supercomputing Service (http://www.archer2.ac.uk).

Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
General Energy
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

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Sohail, B., Blowey, P. J., Rochford, L. A., Ryan, P. T. P., Duncan, D. A., Lee, T. L., Starrs, P., Costantini, G., Woodruff, D. P., & Maurer, R. J. (2023). Donor-Acceptor Co-Adsorption Ratio Controls the Structure and Electronic Properties of Two-Dimensional Alkali-Organic Networks on Ag(100). Journal of Physical Chemistry C, 127(5), 2716-2727. https://doi.org/10.1021/acs.jpcc.2c08688

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title = "Donor-Acceptor Co-Adsorption Ratio Controls the Structure and Electronic Properties of Two-Dimensional Alkali-Organic Networks on Ag(100)",

abstract = "The results are presented of a detailed combined experimental and theoretical investigation of the influence of coadsorbed electron-donating alkali atoms and the prototypical electron acceptor molecule 7,7,8,8-tetracyanoquinodimethane (TCNQ) on the Ag(100) surface. Several coadsorption phases were characterized by scanning tunneling microscopy, low-energy electron diffraction, and soft X-ray photoelectron spectroscopy. Quantitative structural data were obtained using normal-incidence X-ray standing wave (NIXSW) measurements and compared with the results of density functional theory (DFT) calculations using several different methods of dispersion correction. Generally, good agreement between theory and experiment was achieved for the quantitative structures, albeit with the prediction of the alkali atom heights being challenging for some methods. The adsorption structures depend sensitively on the interplay of molecule-metal charge transfer and long-range dispersion forces, which are controlled by the composition ratio between alkali atoms and TCNQ. The large difference in atomic size between K and Cs has negligible effects on stability, whereas increasing the ratio of K/TCNQ from 1:4 to 1:1 leads to a weakening of molecule-metal interaction strength in favor of stronger ionic bonds within the two-dimensional alkali-organic network. A strong dependence of the work function on the alkali donor-TCNQ acceptor coadsorption ratio is predicted.",

author = "B. Sohail and Blowey, {P. J.} and Rochford, {L. A.} and Ryan, {P. T.P.} and Duncan, {D. A.} and Lee, {T. L.} and P. Starrs and G. Costantini and Woodruff, {D. P.} and Maurer, {R. J.}",

note = "Funding Information: The authors thank Diamond Light Source for allocations SI17261 and SI20785 of beam time at beamline I09 that contributed to the results presented here. P.T.P.R. and P.J.B. acknowledge financial support from Diamond Light Source and EPSRC. G.C. acknowledges financial support from the EU through the ERC Grant “VISUAL-MS” (Project ID: 308115). B.S. and R.J.M. acknowledge doctoral studentship funding from the EPSRC and the National Productivity Investment Fund (NPIF). R.J.M. acknowledges financial support via a UKRI Future Leaders Fellowship (MR/S016023/1). The authors acknowledge computing resources provided by the EPSRC-funded HPC Midlands+ Computing Centre (EP/P020232/1 and EP/T022108/1) and the EPSRC-funded Materials Chemistry Consortium (EP/R029431/1) for the ARCHER2 U.K. National Supercomputing Service (http://www.archer2.ac.uk). Publisher Copyright: {\textcopyright} 2023 The Authors. Published by American Chemical Society.",

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doi = "10.1021/acs.jpcc.2c08688",

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Sohail, B, Blowey, PJ, Rochford, LA, Ryan, PTP, Duncan, DA, Lee, TL, Starrs, P, Costantini, G, Woodruff, DP & Maurer, RJ 2023, 'Donor-Acceptor Co-Adsorption Ratio Controls the Structure and Electronic Properties of Two-Dimensional Alkali-Organic Networks on Ag(100)', Journal of Physical Chemistry C, vol. 127, no. 5, pp. 2716-2727. https://doi.org/10.1021/acs.jpcc.2c08688

TY - JOUR

T1 - Donor-Acceptor Co-Adsorption Ratio Controls the Structure and Electronic Properties of Two-Dimensional Alkali-Organic Networks on Ag(100)

AU - Sohail, B.

AU - Blowey, P. J.

AU - Rochford, L. A.

AU - Ryan, P. T.P.

AU - Duncan, D. A.

AU - Lee, T. L.

AU - Starrs, P.

AU - Costantini, G.

AU - Woodruff, D. P.

AU - Maurer, R. J.

N1 - Funding Information: The authors thank Diamond Light Source for allocations SI17261 and SI20785 of beam time at beamline I09 that contributed to the results presented here. P.T.P.R. and P.J.B. acknowledge financial support from Diamond Light Source and EPSRC. G.C. acknowledges financial support from the EU through the ERC Grant “VISUAL-MS” (Project ID: 308115). B.S. and R.J.M. acknowledge doctoral studentship funding from the EPSRC and the National Productivity Investment Fund (NPIF). R.J.M. acknowledges financial support via a UKRI Future Leaders Fellowship (MR/S016023/1). The authors acknowledge computing resources provided by the EPSRC-funded HPC Midlands+ Computing Centre (EP/P020232/1 and EP/T022108/1) and the EPSRC-funded Materials Chemistry Consortium (EP/R029431/1) for the ARCHER2 U.K. National Supercomputing Service (http://www.archer2.ac.uk). Publisher Copyright: © 2023 The Authors. Published by American Chemical Society.

PY - 2023/2/9

Y1 - 2023/2/9

N2 - The results are presented of a detailed combined experimental and theoretical investigation of the influence of coadsorbed electron-donating alkali atoms and the prototypical electron acceptor molecule 7,7,8,8-tetracyanoquinodimethane (TCNQ) on the Ag(100) surface. Several coadsorption phases were characterized by scanning tunneling microscopy, low-energy electron diffraction, and soft X-ray photoelectron spectroscopy. Quantitative structural data were obtained using normal-incidence X-ray standing wave (NIXSW) measurements and compared with the results of density functional theory (DFT) calculations using several different methods of dispersion correction. Generally, good agreement between theory and experiment was achieved for the quantitative structures, albeit with the prediction of the alkali atom heights being challenging for some methods. The adsorption structures depend sensitively on the interplay of molecule-metal charge transfer and long-range dispersion forces, which are controlled by the composition ratio between alkali atoms and TCNQ. The large difference in atomic size between K and Cs has negligible effects on stability, whereas increasing the ratio of K/TCNQ from 1:4 to 1:1 leads to a weakening of molecule-metal interaction strength in favor of stronger ionic bonds within the two-dimensional alkali-organic network. A strong dependence of the work function on the alkali donor-TCNQ acceptor coadsorption ratio is predicted.

AB - The results are presented of a detailed combined experimental and theoretical investigation of the influence of coadsorbed electron-donating alkali atoms and the prototypical electron acceptor molecule 7,7,8,8-tetracyanoquinodimethane (TCNQ) on the Ag(100) surface. Several coadsorption phases were characterized by scanning tunneling microscopy, low-energy electron diffraction, and soft X-ray photoelectron spectroscopy. Quantitative structural data were obtained using normal-incidence X-ray standing wave (NIXSW) measurements and compared with the results of density functional theory (DFT) calculations using several different methods of dispersion correction. Generally, good agreement between theory and experiment was achieved for the quantitative structures, albeit with the prediction of the alkali atom heights being challenging for some methods. The adsorption structures depend sensitively on the interplay of molecule-metal charge transfer and long-range dispersion forces, which are controlled by the composition ratio between alkali atoms and TCNQ. The large difference in atomic size between K and Cs has negligible effects on stability, whereas increasing the ratio of K/TCNQ from 1:4 to 1:1 leads to a weakening of molecule-metal interaction strength in favor of stronger ionic bonds within the two-dimensional alkali-organic network. A strong dependence of the work function on the alkali donor-TCNQ acceptor coadsorption ratio is predicted.

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U2 - 10.1021/acs.jpcc.2c08688

DO - 10.1021/acs.jpcc.2c08688

M3 - Article

AN - SCOPUS:85147157772

SN - 1932-7447

VL - 127

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Donor-Acceptor Co-Adsorption Ratio Controls the Structure and Electronic Properties of Two-Dimensional Alkali-Organic Networks on Ag(100)

Abstract

Bibliographical note

ASJC Scopus subject areas

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