Capturing the Elusive Curve-Crossing in Low-Lying States of Butadiene with Dressed TDDFT

Abstract

A striking example of the need to accurately capture states of double-excitation character in molecules is seen in predicting photoinduced dynamics in small polyenes. Due to the coupling of electronic and nuclear motions, the dark 2¹Ag state, known to have double-excitation character, can be reached after an initial photoexcitation to the bright 1¹Bu state via crossings of their potential energy surfaces. However, the shapes of the surfaces are so poorly captured by most electronic structure methods, that the crossing is missed or substantially mis-located. We demonstrate that the frequency-dependent kernel of dressed TDDFT beyond Tamm-Dancoff successfully captures the curve-crossing, providing an energy surface close to the highly accurate but more expensive δ-CR-EOMCC(2,3) benchmark reference. This, along with its accurate prediction of the excitation character of the state makes dressed TDDFT a practical and accurate route to electronic structure quantities needed in modeling ultrafast dynamics in molecules.