Selected Columns of the Density Matrix in an Atomic Orbital Basis I: An Intrinsic and Non-Iterative Orbital Localization Scheme for the Occupied Space

TL;DR

This paper extends the SCDM method to non-orthogonal atomic orbital basis sets, introducing three variants that produce robust, localized molecular orbitals comparable to traditional localization schemes, with potential to improve convergence.

Contribution

The authors develop three new SCDM variants for non-orthogonal basis sets, enabling efficient, non-iterative construction of localized molecular orbitals with improved robustness and chemical intuition.

Findings

SCDM variants produce orbitals comparable to Boys and Pipek-Mezey methods.

Grid-based SCDM-G preserves symmetry and chemical intuition.

SCDM orbitals can serve as effective initial guesses for localization algorithms.

Abstract

We extend the selected columns of the density matrix (SCDM) methodology [J. Chem. Theory Comput. 2015, 11, 1463--1469]---a non-iterative procedure for generating localized occupied orbitals for condensed-phase systems---to the construction of local molecular orbitals (LMOs) in systems described using non-orthogonal atomic orbital (AO) basis sets. In particular, we introduce three different variants of SCDM (referred to as SCDM-M, SCDM-L, and SCDM-G) that can be used in conjunction with the standard AO basis sets. The SCDM-M and SCDM-L variants are based on the Mulliken and L{\"o}wdin representations of the density matrix, and are tantamount to selecting a well-conditioned set of projected atomic orbitals (PAOs) and projected (symmetrically-) orthogonalized atomic orbitals (POAOs), respectively, as proto-LMOs. The SCDM-G variant leverages a real-space (grid) representation of the wavefunction to select a set of well-conditioned proto-LMOs. A detailed comparative analysis reveals that the LMOs generated by these three SCDM variants are robust, comparable in orbital locality to those produced with the iterative Boys or Pipek-Mezey (PM) localization schemes, and are agnostic towards any single orbital locality metric. Although all three SCDM variants are based on the density matrix, we find that the character of the generated LMOs can differ significantly between SCDM-M, SCDM-L, and SCDM-G. In this regard, only the grid-based SCDM-G procedure (like PM) generates LMOs that qualitatively preserve $\sigma\text{-}\pi$ symmetry and are well-aligned with chemical intuition. While the direct and standalone use of SCDM-generated LMOs should suffice for most applications, our findings also suggest that the use of these orbitals as an unbiased and cost-effective (initial) guess also has the potential to improve the convergence of iterative orbital localization schemes.