A Wannier-first approach for extended chiral systems

Abstract

We present a real-space formulation of density functional theory for extended systems in which localized Wannier-like functions are constructed directly from localized Gaussian basis functions without explicitly computing canonical Bloch-like states during the self-consistent cycle. Building on the formalism of Pederson and Lin [Phys. Rev. B 35, 2273 (1987)], a variational set of Wannier-like functions is generated self-consistently within a finite Wannier domain and used to construct the charge density, electrostatic potential, and per cell total energy of the extended system. The occupied space can be determined entirely from the Wannier-like functions. Electronic band structures can be recovered in a post-processing step by solving the full Hamiltonian in a Bloch-like basis constructed from Gaussian orbitals. A key feature of the method is that it can incorporate combined translation–rotation, or screw, symmetries, enabling efficient simulations of chiral and helical systems with finite twist angles at essentially the same computational cost as systems described by pure translational symmetry. The approach is validated through calculations on linear and twisted –C≡C– and –Li–F– chains, as well as graphene, where total energies and band structures show excellent agreement with reference periodic calculations. To illustrate the ability of the method to treat three-dimensional systems, it is further applied to AA graphite, in which carbon atoms in adjacent graphene layers are aligned directly above one another, as well as helically stacked AA graphite structures. The Wannier-first framework provides a practical route for treating extended systems with non-trivial translational, rotational, and screw symmetries, and provides a natural foundation for the implementation of orbital-dependent functionals such as the Perdew–Zunger self-interaction correction.