The Wiedemann-Franz (WF) law is a fundamental result in solid-state physics that relates the thermal and electrical conductivity of a metal. It is derived from the predominant origin of energy conversion in metals: the motion of quasi-free charge-carrying particles. In this talk, I will discuss the development and application of an equivalent WF relationship for molecular systems in which charge carriers are moving not as free particles but instead hop between redox sites. We derive a concise analytical relationship between the electrical and thermal conductivity generated by electron hopping in molecular systems and find that the linear temperature dependence of their ratio as expressed in the standard WF law is replaced by a linear dependence on the nuclear reorganization energy associated with the electron hopping process. We term this ratio a <i>molecular </i>Wiedemann-Franz (MWF) law, in analogy with the WF law for metals. The robustness of the MWF law is confirmed by examining the conductance properties of a model molecular junction.

Wiedemann-Franz law for molecules

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.