Theory and applications of generalized Pipek--Mezey Wannier functions

TL;DR

This paper introduces a generalized Pipek--Mezey approach for generating highly localized Wannier functions, compares it with the traditional MLWF method, and demonstrates its implementation across various systems and software platforms.

Contribution

The paper presents a new generalized Pipek--Mezey Wannier functions method, its implementation, and comparison with MLWF, highlighting improved orbital localization and compatibility with multiple computational frameworks.

Findings

PMWF are as localized as MLWFs

PMWF maintain chemical intuition with clear orbital distinctions

Implementation supports various wave function representations

Abstract

The theory for the generation of Wannier functions within the generalized Pipek--Mezey approach [Lehtola, S.; J\'onsson, H. J. Chem. Theory Comput. 2014, 10, 642] is presented and an implementation thereof is described. Results are presented for systems with periodicity in one, two and three dimensions as well as isolated molecules. The generalized Pipek--Mezey Wannier functions (PMWF) are highly localized orbitals consistent with chemical intuition where a distinction is maintained between {\sigma}- and {\pi}-orbitals. The PMWF method is compared with the so-called maximally localized Wannier functions (MLWF) that are frequently used for the analysis of condensed matter calculations. Whereas PMWFs maximize the localization criterion of Pipek and Mezey, MLWFs maximize that of Foster and Boys and have the disadvantage of mixing {\sigma}- and {\pi}-orbitals in many cases. The PMWF orbitals turn out to be as localized as the MLWF orbitals as evidenced by cross-comparison of the values of the PMWF and MLWF objective functions for the two types of orbitals. Our implementation in the atomic simulation environment (ASE) is compatible with various representations of the wave function, including real-space grids, plane waves and linear combinations of atomic orbitals. The projector augmented wave formalism for the representation of atomic core electrons is also supported. Results of calculations with the GPAW software are described here, but our implementation can also use output from other electronic structure software such as ABINIT, NWChem and VASP.