Molecular Excited States: Accurate Calculation of Relative Energies and Electronic Coupling Between Charge Transfer and Non-Charge Transfer States

We show for a series of six small donor–acceptor dyads that the energy difference between non-charge transfer (non-CT) and charge transfer (CT) excited states, as well as the squares of the electronic couplings between these states, can be predicted from first-principles using variational orbital adapted configuration interaction singles (VOA-CIS) theory. VOA-CIS correctly predicts the observed experimental trends in these values and provides quantitative accuracy roughly on par with a modern long-range corrected density functional, ωB97X. Using VOA-CIS and ωB97X, the experimental energy difference between the non-CT and CT excited states is predicted with root mean squared errors of 0.22 eV and 0.21 eV, respectively. The square of the electronic coupling between these states is predicted with root mean squared errors of 0.08 eV2 and 0.07 eV2, respectively. Here, orbital optimized CIS (OO-CIS) and CIS(D), two perturbative corrections to CIS, provide a significant correction to the errant relative energies predicted by CIS, but the correction is insufficient to recover the experimentally observed trend.