TDDFT Study of One- and Two-Photon Absorption Properties:  Donor−π−Acceptor Chromophores

Abstract

We report a comprehensive time-dependent density functional theory (TDDFT) study of one-photon and two-photon absorption (OPA and TPA, respectively) spectra for donor−π−acceptor molecules. The calculated excitation energies were generally shown to be in good agreement with experiment, particularly when compared to results from measurements carried out in a nonpolar solvent, although the oscillator strengths were overestimated in some cases. Calculated TPA cross sections applying the two-state approximation were shown to be highly dependent on the form of the line-shape function used. Although a good agreement with experimental TPA spectra was generally observed, the wide range in the experimentally measured values and lack of systematic experimental data on solvent effects limited a detailed comparison as yet.