Proton Quantum Effects on Electronic Excitation in Hydrogen-Bonded Organic Solid: A First-Principles Green’s Function Theory Study

Nuclear quantum effects of protons on electronic excitations in hydrogen-bonded organic materials remains underexplored. In theoretical studies, modeling excitons in these extended systems is particularly difficult, because they tend to have a large exciton binding energy and sometimes exhibit charge transfer character. We demonstrate how first-principles Green’s function theory combined with the nuclear-electronic orbital method enables us to examine the nature of excitons in a prototypical organic solid of eumelanin, for which extensive hydrogen bonds have been proposed to facilitate the formation of delocalized excitons. We investigate how the quantization of protons impacts electronic excitations. We discuss the extent to which the resulting proton quantum effects can be described as being derived from the structure and how they induce molecular-level anisotropy for the excitons in the organic solid.