Transition from stochastic events to deterministic ensemble average in electron transfer reactions revealed by single-molecule conductance measurement

Yueqi Li, Hui Wang, Zixiao Wang, Yanjun Qiao, Jens Ulstrup, Hong Yuan Chen, Gang Zhou, Nongjian Tao

Research output: Contribution to journalArticle

7 Scopus citations

Abstract

Electron transfer reactions can now be followed at the single-molecule level, but the connection between the microscopic and macroscopic data remains to be understood. By monitoring the conductance of a single molecule, we show that the individual electron transfer reaction events are stochastic and manifested as large conductance fluctuations. The fluctuation probability follows first-order kinetics with potential dependent rate constants described by the Butler–Volmer relation. Ensemble averaging of many individual reaction events leads to a deterministic dependence of the conductance on the external electrochemical potential that follows the Nernst equation. This study discloses a systematic transition from stochastic kinetics of individual reaction events to deterministic thermodynamics of ensemble averages and provides insights into electron transfer processes of small systems, consisting of a single molecule or a small number of molecules.

Original languageEnglish (US)
Pages (from-to)3407-3412
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Volume116
Issue number9
DOIs
StatePublished - Feb 26 2019

Keywords

  • Electron transfer reactions
  • Ensemble averaging
  • Molecular electronics
  • Single molecule
  • Stochastic electron transfer

ASJC Scopus subject areas

  • General

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