Projected Commutator DIIS Method for Accelerating Hybrid Functional Electronic Structure Calculations

TL;DR

This paper introduces the projected commutator DIIS (PC-DIIS) method, enabling efficient convergence acceleration in large basis set electronic structure calculations, especially for hybrid functional DFT, with performance surpassing traditional methods.

Contribution

The paper develops a gauge-invariant, projection-based extension of the C-DIIS method suitable for large basis sets, improving convergence in hybrid functional electronic structure calculations.

Findings

PC-DIIS operates with cost comparable to standard charge mixing.

The method is gauge-invariant and unitary transformation independent.

PC-DIIS outperforms nested two-level SCF iteration procedures.

Abstract

The commutator direct inversion of the iterative subspace (commutator DIIS or C-DIIS) method developed by Pulay is an efficient and the most widely used scheme in quantum chemistry to accelerate the convergence of self consistent field (SCF) iterations in Hartree-Fock theory and Kohn-Sham density functional theory. The C-DIIS method requires the explicit storage of the density matrix, the Fock matrix and the commutator matrix. Hence the method can only be used for systems with a relatively small basis set, such as the Gaussian basis set. We develop a new method that enables the C-DIIS method to be efficiently employed in electronic structure calculations with a large basis set such as planewaves for the first time. The key ingredient is the projection of both the density matrix and the commutator matrix to an auxiliary matrix called the gauge-fixing matrix. The resulting projected commutator-DIIS method (PC-DIIS) only operates on matrices of the same dimension as the that consists of Kohn-Sham orbitals. The cost of the method is comparable to that of standard charge mixing schemes used in large basis set calculations. The PC-DIIS method is gauge-invariant, which guarantees that its performance is invariant with respect to any unitary transformation of the Kohn-Sham orbitals. We demonstrate that the PC-DIIS method can be viewed as an extension of an iterative eigensolver for nonlinear problems. We use the PC-DIIS method for accelerating Kohn-Sham density functional theory calculations with hybrid exchange-correlation functionals, and demonstrate its superior performance compared to the commonly used nested two-level SCF iteration procedure.