Abstract
Electron transfer dominates chemical processes in biological, inorganic, and material chemistry. Energetic aspects of such phenomena, in particular, the energy transfer associated with the electron transfer process, have received little attention in the past but are important in designing energy conversion devices. This paper generalizes our earlier work in this direction, which was based on the semiclassical Marcus theory of electron transfer. It provides, within a simple model, a unified framework that includes the deep (nuclear) tunneling limit of electron transfer and the associated heat transfer when the donor and acceptor sites are seated in environments characterized by different local temperatures. The electron transfer induced heat conduction is shown to go through a maximum at some intermediate average temperature where quantum effects are already appreciable, and it approaches zero when the average temperature is very high (the classical limit) or very low (deep tunneling).
Highlights
Electron transfer (ET) processes lie at the core of oxidation-reduction reactions, ranging from photosynthesis [1] to electrochemistry [2], corrosion [3] and vision [4], and are key ingredients in many subjects of present research, such as photoelectrochemistry [5], solar energy conversion [6], organic light-emitting diodes [7], and molecular electronic devices [8].Despite its inherent limitations, the Marcus theory is the most commonly used approach used for understanding such phenomena [9, 10]
The Marcus expression for the electron transfer rate is the high temperature limit of a more general expression obtained by Jortner and coworkers from the golden-rule calculation of the rate [11,12,13,14], which can account for nuclear tunneling at low temperatures
We have generalized our earlier theory of electron-transfer induced heat transfer (ETIHT) that was developed under the Marcus high-temperature approximation, to the low temperature regime, using a calculation based on the Fermi’s golden rule approach
Summary
Electron transfer (ET) processes lie at the core of oxidation-reduction reactions, ranging from photosynthesis [1] to electrochemistry [2], corrosion [3] and vision [4], and are key ingredients in many subjects of present research, such as photoelectrochemistry [5], solar energy conversion [6], organic light-emitting diodes [7], and molecular electronic devices [8]. Two of us have addressed this problem by generalizing the standard Marcus theory of electron transfer between two molecular sites or between a molecule and a metal, to account for situations in which different sites are characterized by different local temperatures [39, 40]. This generalization of Marcus theory leads to a modified expression for the electron transfer rate in terms of the different site temperatures as well as a way to calculate the heat transfer associated with the electron transfer process.
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