We present a computational investigation of the conformational response of phycocyanobilin (PCB) to the ability of solvents to form hydrogen bonds. PCB is the chromophore of several proteins in light harvesting complexes. We determine the conformational distributions in different solvents (methanol and hexamethylphosphoramide HMPT) by means of ab initio molecular dynamics simulations and characterize them via ab initio calculations of NMR chemical shift patterns. The computed trajectories and spectroscopic fingerprints illustrate that the energy landscape is very complex and exhibits various conformations of similar energy. We elucidate the strong influence of the solvent characteristics on the structural and spectroscopic parameters. Specifically, we predict a cis–trans isomerization of phycocyanobilin upon switching from the aprotic to the protic solvent, which explains an experimentally observed change in the NMR patterns. In the context of technological molecular recognition, solvent induced conformational switching can be considered a precursor mechanism to the recognition of single molecules.
