Propagated (fragment) Pipek–Mezey Wannier functions in real-time time-dependent density functional theory

Abstract

Localization procedures are an important tool for analysis of complex systems in quantum chemistry, since canonical molecular orbitals are delocalized and can, therefore, be difficult to align with chemical intuition and obscure information at the local level of the system. This especially applies to calculations obeying periodic boundary conditions. The most commonly used approach to localization is Foster–Boys Wannier functions, which use a unitary transformation to jointly minimize the second moment of the orbitals. This procedure has proven to be robust and fast but has a side effect of often mixing σ- and π-type orbitals. σ/π-separation is achieved by the Pipek–Mezey Wannier function (PMWF) approach [Lehtola and Jónsson, J. Chem. Theory Comput. 10, 642 (2014) and Jónsson et al., J. Chem. Theory Comput. 13, 460 (2017)], which defines the spread functional in terms of partial charges instead. We have implemented a PMWF algorithm in the CP2K software package using the Cardoso–Souloumiac algorithm to enable their application to real-time time-dependent density functional theory. The method is demonstrated on stacked CO2 molecules, linear acetylenic carbon, boron and nitrogen co-doped graphene, and nitrogen-vacancy doped diamond. Finally, we discuss its computational scaling and recent efforts to improve it with fragment approaches.