Analytical description of the consequences of abandoning the principles of detailed balance and microscopic reversibility in semiconductor photoelectrochemistry

Gary A. Shreve, Nathan S Lewis

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Key differences between the conventional and 'irreversible' models of semiconductor photoelectrochemistry are identified and discussed within the framework of experimental observations. Conceptual differences between these two models appear to lie in the treatment of interfacial charge-transfer processes for photogenerated charge carriers. The conventional model utilizes detailed balance principles for obtaining rate constant relationships for all interfacial charge-transfer events at semiconductor/liquid contacts and uses the principle of microscopic reversibility to evaluate these rate constants for situations away from equilibrium. In contrast, the irreversible model postulates that local statistical detailed balance does not apply to charge-transfer events in photoelectrolysis, and that such charge-transfer events are highly irreversible, like photoemission into a vacuum. It is shown analytically that the two models predict differences in the behavior of the available free energy produced by a photoelectrochemical cell at a fixed incident light intensity. The conceptual implications of these differences are evaluated analytically and are also compared to experimental results for semiconductor/liquid junctions.

Original languageEnglish
Pages (from-to)112-119
Number of pages8
JournalJournal of the Electrochemical Society
Volume142
Issue number1
Publication statusPublished - Jan 1995

Fingerprint

photoelectrochemistry
Charge transfer
Semiconductor materials
charge transfer
Rate constants
Photoelectrochemical cells
Liquids
Photoemission
liquids
axioms
Charge carriers
Contacts (fluid mechanics)
luminous intensity
Free energy
charge carriers
photoelectric emission
free energy
Vacuum
vacuum
cells

ASJC Scopus subject areas

  • Electrochemistry
  • Surfaces, Coatings and Films
  • Surfaces and Interfaces

Cite this

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