Anomalous behavior of native point defects in C2-ordered antiferromagnet $α$-MnO$_2$

Abstract: $α$-MnO$<em>2$ is an emerging material for electronic, optoelectronic, and energy applications, owing to its structural flexibility and defect-driven functionality. During synthesis of $α$-MnO$_2$, native oxygen vacancies readily form and are typically compensated by foreign dopants. A thorough understanding of intrinsic defects is therefore essential for enabling controlled extrinsic doping and optimizing material performance. Using density functional approach, we investigate the structural, electronic, magnetic, and optical properties of the ground state C2-type antiferromagnetic $α$-MnO$_2$ in the presence of native point defects, including interstitials, vacancies, and antisites. We compute their thermodynamic stability, incorporating electrostatic corrections to eliminate spurious long-range interactions. Mn interstitial (Mn$</em>\text{i}$) and Mn antisite O (Mn$<em>\text{O}$) introduce shallow donor levels, whereas O-vacancy (V$</em>\text{O}$) exhibit amphoteric behavior and act as compensating centers. The calculated defect formation energies reveal pronounced competition between donor- and acceptor-type native defects, leading to strong intrinsic defect compensation under both Mn-rich and O-rich growth conditions. Mn vacancy (V$<em>\text{Mn}$) remains ionized across the band gap and behaves as a shallow acceptor, suggesting its potential role under suitable non-equilibrium growth conditions, whereas O antisite Mn (O$</em>\text{Mn}$) forms deep acceptor levels. BSE@G$_0$W_0$$calculations reveal a strongly anisotropic optical response in stoichiometric$$α$-MnO$_2$, while native point defects introduce pronounced sub-gap excitations and enhanced dielectric screening, with vacancies producing the largest effect.