TD‐DFT modeling of electronic spectra of biliverdins in different environments

Non covalent biliproteins are found in a growing number of living organisms and even in viruses, such as SARS‐CoV‐2. Unlike the well described covalent biliproteins, such as the phytochromes, they present a vast structural and functional diversity, and often with limited experimental information. A very important tool (and sometimes the only one available) to study these systems is the UV–Vis spectrum, which is modulated both by conformational changes of the biliverdin chromophore and specific interactions with the apoprotein. In this work we present a theoretical study of the microscopic determinants of the UV–Vis spectrum of these compounds through the use of hybrid QM(TD‐DFT)/MM techniques and molecular dynamics simulations. Comparing our results with existing experimental data, we prove that it is possible to predict spectroscopic properties, such as relative position and intensity ratio of main bands, with affordable methods, and to provide a microscopic explanation of them. This systematic information can be very useful for the study of described biliproteins or for those yet unknown. Biliverdins in different conformations and the corresponding UV‐visible spectrum.