Effects of torsional disorder and position isomerism on two-photon absorption properties of polar chromophore dimers

Two-photon absorption properties of a push-pull molecule and its covalent dimers have been studied by density functional response theory in combination with polarizable continuum model. A set of constrained geometries with different torsional angles are optimized and used to calculate two-photon absorption spectra. It is found that the torsional disorder could possibly produce the experimental two-photon absorption additive behavior. We have also designed a series of covalent dimers and investigated the effects of position isomerism. Our results suggest that the cooperative two-photon absorption enhancement can be achieved when the subunits are substituted in closer proximity and have larger interchromophore angle.