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On the theory of charge transport and entropic effects in solvated molecular junctions

Sowa, Jakub K. and Marcus, Rudolph A. (2021) On the theory of charge transport and entropic effects in solvated molecular junctions. Journal of Chemical Physics, 154 (3). Art. No. 034110. ISSN 0021-9606. https://resolver.caltech.edu/CaltechAUTHORS:20210127-125542902

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Abstract

Experimental studies on single-molecule junctions are typically in need of a simple theoretical approach that can reproduce or be fitted to experimentally measured transport data. In this context, the single-level variant of the Landauer approach is most commonly used, but methods based on Marcus theory are also gaining popularity. Recently, a generalized theory unifying these two approaches has also been developed. In the present work, we extend this theory so that it includes entropic effects (which can be important when polar solvents are involved but are likely minor for solid-state systems). We investigate the temperature-dependence of the electric current and compare it to the behavior predicted by the Landauer and the conventional Marcus theory. We argue that this generalized theory provides a simple yet effective framework for understanding charge transport through molecular junctions. Furthermore, we explore the role of the entropic effects in different transport regimes and suggest experimental criteria for detecting them in solvated molecular junctions. Finally, in order to account for nuclear tunneling effects, we also demonstrate how lifetime broadening can be introduced into the Marcus–Levich–Dogonadze–Jortner-type description of electron transport.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1063/5.0034782DOIArticle
ORCID:
AuthorORCID
Sowa, Jakub K.0000-0003-4104-2664
Marcus, Rudolph A.0000-0001-6547-1469
Additional Information:© 2021 Published under license by AIP Publishing. Submitted: 22 October 2020; Accepted: 29 December 2020; Published Online: 21 January 2021. J.K.S. thanks Hertford College, Oxford, for financial support and L. MacGregor for carefully reading the manuscript. R.A.M. thanks the Office of the Naval Research and the Army Research Office for their support of this research. Data Availability: The data that support the findings of this study are available within the article itself.
Funders:
Funding AgencyGrant Number
Hertford CollegeUNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Issue or Number:3
Record Number:CaltechAUTHORS:20210127-125542902
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210127-125542902
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:107775
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:27 Jan 2021 21:02
Last Modified:27 Jan 2021 21:02

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