Calculating the spectroscopic properties of complex conjugated organic molecules in their relaxed state is far from simple. An additional complexity arises for flexible molecules in solution, where the rotational energy barriers are low enough so that nonminimum conformations may become dynamically populated. These metastable conformations quickly relax during the minimization procedures preliminary to density functional theory calculations, and so accounting for their contribution to the experimentally observed properties is problematic. We describe a strategy for stabilizing these nonminimum conformations in silico, allowing their properties to be calculated. Diadinoxanthin and alloxanthin present atypical vibrational properties in solution, indicating the presence of several conformations. Performing energy calculations in vacuo and polarizable continuum model calculations in different solvents, we found three different conformations with values for the δ dihedral angle of the end ring ca. 0, 180, and 90° with respect to the plane of the conjugated chain. The latter conformation, a nonglobal minimum, is not stable during the minimization necessary for modeling its spectroscopic properties. To circumvent this classical problem, we used a Car-Parinello MD supermolecular approach, in which diadinoxanthin was solvated by water molecules so that metastable conformations were stabilized by hydrogen-bonding interactions. We progressively removed the number of solvating waters to find the minimum required for this stabilization. This strategy represents the first modeling of a carotenoid in a distorted conformation and provides an accurate interpretation of the experimental data.

Biology Centre Czech Academy of Sciences Branisovska 31 370 05 Ceske Budejovice Czech Republic

Faculty of Science University of South Bohemia Branisovska 1760 370 05 Ceske Budejovice Czech Republic

Institute of Chemical Physics Faculty of Physics Vilnius University Saulėtekio Ave 3 LT 10222 Vilnius Lithuania

Institute of Microbiology Academy of Sciences of the Czech Republic 379 81 Třeboň Czech Republic

Key Laboratory of Photobiology Institute of Botany Chinese Academy of Sciences 100093 Beijing People's Republic of China

Molecular Compounds Physics Department Center for Physical Sciences and Technology Sauletekio Ave 3 LT 10257 Vilnius Lithuania

Université Paris Saclay CEA CNRS Institute for Integrative Biology of the Cell 91198 Gif sur Yvette France

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