Beyond Marcus theory and the Landauer–Büttiker approach in molecular junctions. II. A self-consistent Born approach

Jakub K. Sowa, Neill Lambert, Tamar Seideman, Erik M. Gauger

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Abstract

Marcus and Landauer-Buttiker approaches to charge transport through molecular junctions describe two contrasting mechanisms of electronic conduction. In previous work, we have shown how these charge transport theories can be unified in the single-level case by incorporating lifetime broadening into the second-order quantum master equation. Here, we extend our previous treatment by incorporating lifetime broadening in the spirit of the self-consistent Born approximation. By comparing both theories to numerically converged hierarchical-equations-of-motion (HEOM) results, we demonstrate that our novel self-consistent approach rectifies shortcomings of our earlier framework which are present especially in the case of relatively strong electron-vibrational coupling. We also discuss circumstances under which the theory developed here simplifies to the generalised theory developed in our earlier work. Finally, by considering the high-temperature limit of our new self-consistent treatment, we show how lifetime broadening can also be self-consistently incorporated into Marcus theory. Overall, we demonstrate that the self-consistent approach constitutes a more accurate description of molecular conduction while retaining most of the conceptual simplicity of our earlier framework.
Original languageEnglish
Article number064103
JournalThe Journal of Chemical Physics
Volume152
Issue number6
Early online date10 Feb 2020
DOIs
Publication statusPublished - 14 Feb 2020

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life (durability)
conduction
transport theory
retaining
Born approximation
equations of motion
electronics
electrons

Keywords

  • physics.chem-ph
  • cond-mat.mes-hall

Cite this

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Beyond Marcus theory and the Landauer–Büttiker approach in molecular junctions. II. A self-consistent Born approach. / Sowa, Jakub K.; Lambert, Neill; Seideman, Tamar; Gauger, Erik M.

In: The Journal of Chemical Physics, Vol. 152, No. 6, 064103, 14.02.2020.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Beyond Marcus theory and the Landauer–Büttiker approach in molecular junctions. II. A self-consistent Born approach

AU - Sowa, Jakub K.

AU - Lambert, Neill

AU - Seideman, Tamar

AU - Gauger, Erik M.

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AB - Marcus and Landauer-Buttiker approaches to charge transport through molecular junctions describe two contrasting mechanisms of electronic conduction. In previous work, we have shown how these charge transport theories can be unified in the single-level case by incorporating lifetime broadening into the second-order quantum master equation. Here, we extend our previous treatment by incorporating lifetime broadening in the spirit of the self-consistent Born approximation. By comparing both theories to numerically converged hierarchical-equations-of-motion (HEOM) results, we demonstrate that our novel self-consistent approach rectifies shortcomings of our earlier framework which are present especially in the case of relatively strong electron-vibrational coupling. We also discuss circumstances under which the theory developed here simplifies to the generalised theory developed in our earlier work. Finally, by considering the high-temperature limit of our new self-consistent treatment, we show how lifetime broadening can also be self-consistently incorporated into Marcus theory. Overall, we demonstrate that the self-consistent approach constitutes a more accurate description of molecular conduction while retaining most of the conceptual simplicity of our earlier framework.

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