A computational study of the excited states of bilirubin IX

Abstract

We have determined the lowest excited states of bilirubin IX by TD-DFT calculations. The lowest pair of excited states, S₁ and S₂, turn out to be of charge-transfer (CT) nature. Although DFT based methods tend to underestimate the energy of CT states, the small oscillator strengths we have computed indicate that such states may actually exist in this spectral region, but would have escaped spectroscopic detection. The next pair of excited states, S₃ and S₄, account for the most prominent spectral feature of bilirubin. They can be accurately described by the exciton coupling model, as we show by a thorough analysis of wavefunctions and properties. This finding therefore supports the interpretation of bilirubin photoisomerization behaviour, based on the exciton coupling model.