Phonon-induced electronic degeneracy breaking: a SSAdNDP interpretation

Abstract: This work explores how phonon perturbations can induce the breaking of electronic degeneracies near the Fermi level and how this response can be interpreted from a chemical perspective through the SSAdNDP method. We apply this approach to a family of structurally similar yet electronically distinct hexagonal materials-MgB2, graphene, and hBN-to analyze how a single phonon mode simultaneously modifies the electronic structure (band dispersion) and the nature of chemical bonding (natural occupations and nodal patterns) in real space. Our results show that band splitting becomes physically relevant only when it is accompanied by an electronic redistribution, reflected in changes of the occupation numbers or bonding topology. Thus, SSAdNDP provides a direct bridge between reciprocal- and real-space representations, translating phenomena such as electron-phonon coupling into chemically intuitive reorganizations of multicenter bonds, and offering a unified framework to interpret vibrationally driven electronic effects in solids.