Nature of frontier quasi-particle states in nitrogen-base systems

Abstract

Understanding photophysical properties of DNA is important: It can help us elucidate and probe the impact of charges and free radicals in the cellular environment. For example, a photoemission at a given nucleobase means that we both charge it and place an electron right next to a neighboring part of the genetic code. Inverse photoemission means that we trap a free electron (at some empty state or resonance), and instead emit a low-energy photon. This may reduce the damage if it happens at an already charged base, but it can cause extra damage if it arises somewhere else. Predicting the nature of sudden optically-driven excitations, termed quasi-particles (QPs), help us detail interactions and possibly control the damage that might follow. Also, these QPs contain information on the larger DNA assembly because they reflect the fingerprints of nucleobase polarity, the hydrogen bonding in Watson-Crick pairs, and the van der Waals (vdW) interactions in the Watson-Crick-pair stacking that makes up the genome. In this study, we utilize the recently developed (optimally tuned) range-separated hybrid vdW density functional, AHBR-mRSH* [JPCM 37, 211501 (2025)] to analyze the electron-attached and ionized QP states of these DNA components, with a particular focus on dipole- and multipole-trapped empty states (bound or resonances). We also evaluate critical properties such as dipole and quadrupole moments, QP HOMO-LUMO energy gaps, and transition-dipole moments. Finally, we classify the Watson-Crick stacked dimers based on their QP nature. This classification provides the foundation for proposing a model of DNA reactivity and photo-physical activity.