On the Counter‐intuitive Heterogeneous Electron Transfer Barrier Properties of Alkanethiolate Monolayers on Gold: Smooth versus Rough Surfaces

Green, John‐Bruce D.; Clarke, Eamonn; Porter, Marc D.; McDermott, Christie A.; McDermott, Mark T.; Zhong, Chuan‐Jian; Bergren, Adam Johan

doi:10.1002/elan.202100704

On the Counter‐intuitive Heterogeneous Electron Transfer Barrier Properties of Alkanethiolate Monolayers on Gold: Smooth versus Rough Surfaces

Journal Article · 06 April 2022 · Electroanalysis

DOI:https://doi.org/10.1002/elan.202100704· OSTI ID:2423800

Green, John‐Bruce D. ^[1]; ^[2]; Porter, Marc D. ^[3]; McDermott, Christie A. ^[4]; McDermott, Mark T. ^[4]; Zhong, Chuan‐Jian ^[5]; Bergren, Adam Johan ^[6]

Department of Chemistry Illinois Institute of Technology Chicago IL 60616
Department of Chemistry University of Utah Salt Lake City UT, 84112
Department of Chemistry University of Utah Salt Lake City UT, 84112; Departments of Chemical Engineering and Pathology University of Utah Salt Lake City UT, 84112
Department of Chemistry University of Alberta Edmonton Alberta T6G 2G2
Department of Chemistry State University of New York at Binghamton Binghamton NY 13902
Nanotechnology Research Centre National Research Council of Canada Edmonton AB T6G 2M9 Canada Department of Chemistry University of British Columbia Kelowna BC V1V 1V7 Canada

Abstract

Alkanethiolate monolayers formed on rough gold surfaces can, somewhat surprisingly, act as stronger barriers to heterogeneous electron transfer than those on smooth gold surfaces. This paper presents a possible explanation for this observation by constructing simple geometric models of a “rough” and “smooth” gold surface to examine how microscopic roughness differences can affect the nucleation/growth of the adlayer and size/density of structural defects. Expectedly, the number of defects predicted for adlayers formed on smooth gold is lower than any of those for rough gold. The counter‐intuitive result is that the sizes of a small portion of the defects in the adlayer on the smooth surface are larger than any of those found on the rough surface. The potential implications of these results are discussed.

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC02-07CH11358

OSTI ID:: 2423800

Journal Information:: Electroanalysis, Journal Name: Electroanalysis Journal Issue: 12 Vol. 34; ISSN 1040-0397

Publisher:: Wiley

Country of Publication:: United States

Language:: English

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