Computational study on controlling the optical properties of solar thermal fuels

Abstract

Solar thermal fuels utilize molecules that undergo reversible photo-isomerization to convert solar energy into stored thermal energy.¹ Because solar thermal fuels produce no emissions and can store and convert energy within one material, they are an attractive option for a renewable energy source. However, it has remained a challenge to identify a suitable solar thermal fuel material that exhibits high energy density, high energy conversion efficiency, long energy storage lifetime, and can be produced at low cost. A recent proposal is a nanotemplate-photoisomer hybrid system, e.g. functionalized azobenzene, a well-known photoisomer molecule, attached to carbon nanostructure templates such as carbon nanotubes, graphene, pentacene or alkene chains. Such structures have been suggested and tested as candidate solar thermal fuel materials with high energy density and long storage time²⁻⁴ In this thesis work, we further investigated optical properties of functionalized azobenzene and geometry-modified azobenzene. We found the best structure that yields maximum optical isomerization rate for trans-azobenzene and minimum optical isomerization rate for cis-azobenzene, calculating the reaction rate based on overlap between the solar spectrum and optical spectra calculated using time-dependent density functional theory (TDDFT). We showed that energy-charged-state molecule (cis-isomer) content at the photostationary state can be improved from 73 percent for pure azobenzene to 83 percent and to 97 percent by functionalizing azobenzene and a designing different geometry for azobenzene, respectively. From this, a desired structure for nanotemplates-photoisomer hybrid system can be estimated and same calculation technique may be employed to calculate and optimize photostationary state of the nanotemplates-photoisomer hybrid system.