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Solar thermal fuels (STFs) are an unconventional paradigm for solar energyconversion and storage which is attracting renewed attention. In this concept,a material absorbs sunlight and stores the energy chemically via an inducedstructural change, which can later be reversed to release the energy as heat.An example is the azobenzene molecule which has a cis-trans photoisomerizationwith these properties, and can be tuned by chemical substitution and attachmentto templates such as carbon nanotubes, small molecules, or polymers. By analogyto the Shockley-Queisser limit for photovoltaics, we analyze the maximumattainable efficiency for STFs from fundamental thermodynamic considerations.Microscopic reversibility provides a bound on the quantum yield ofphotoisomerization due to fluorescence, regardless of details ofphotochemistry. We emphasize the importance of analyzing the free energy, notjust enthalpy, of the metastable molecules, and find an efficiency limit forconversion to stored chemical energy equal to the Shockley-Queisser limit. STFcandidates from a recent high-throughput search are analyzed in light of theefficiency limit.

Thermodynamic limits to energy conversion in solar thermal fuels