TAO-DFT with the Polarizable Continuum Model

For the ground-state properties of gas-phase nanomolecules with multi-reference character, thermally assisted occupation (TAO) density functional theory (DFT) has recently been found to outperform the widely used Kohn-Sham DFT when traditional exchange-correlation energy functionals are employed. Aiming to explore solvation effects on the ground-state properties of nanomolecules with multi-reference character at a minimal computational cost, we combined TAO-DFT with the PCM (polarizable continuum model). In order to show its usefulness, TAO-DFT-based PCM (TAO-PCM) was used to predict the electronic properties of linear acenes in three different solvents (toluene, chlorobenzene, and water). According to TAO-PCM, in the presence of these solvents, the smaller acenes should have nonradical character, and the larger ones should have increasing polyradical character, revealing striking similarities to the past findings in the gas phase.

Automated summary

By combining TAO-DFT with the PCM model, solvation effects on the ground-state properties of nanomolecules with multi-reference character can be explored at a minimal computational cost. The TAO-PCM model was used to predict the electronic properties of linear acenes in different solvents (toluene, chlorobenzene, and water). According to the TAO-PCM model, in the presence of these solvents, smaller acenes should exhibit nonradical character, while larger acenes should exhibit increasing polyradical character, showing similarity to previous gas-phase studies.