Calculating excited states of molecular aggregates by the renormalized excitonic method.

ABSTRACT

In this paper, we apply the recently developed ab initio renormalized excitonic method (REM) to the excitation energy calculations of various molecular aggregates, through the extension of REM to the time-dependent density functional theory (TDDFT). Tested molecular aggregate systems include one-dimensional hydrogen-bonded water chains, ring crystals with π-π stacking or van der Waals interactions, two dimensional benzene aggregates and the general aqueous systems with polar and nonpolar solutes. The basis set factor as well as the effect of the exchange-correlation functionals are also investigated. The results indicate that the REM-TDDFT method with suitable basis set and exchange-correlation functionals can give good descriptions of excitation energies and excitation area for lowest electronic excitations in the molecular aggregate systems with economic computational costs. It is shown that the deviations of REM-TDDFT excitation energies from those by standard TDDFT are much less than 0.1 eV and the computational time can be reduced by one order.