Direct Unconstrained Optimization of Molecular Orbital Coefficients in Density Functional Theory

Abstract

One-electron orbitals in Kohn–Sham density functional theory (DFT) are typically constrained to be orthogonal during their variational optimization, leading to elaborate parameterization of the orbitals and complicated optimization algorithms. This work shows that orbital optimization can be performed with nonorthogonal orbitals if the DFT energy functional is augmented with a term that penalizes linearly dependent states. This approach, called variable-metric self-consistent field (VM SCF) optimization, allows us to use molecular orbital coefficients, natural descriptors of one-electron orbitals, as independent variables in a direct, unconstrained minimization, leading to very simple closed-form expressions for the electronic gradient and Hessian. It is demonstrated that efficient convergence of the VM SCF procedure can be achieved with a basic preconditioned conjugate gradient algorithm for a variety of systems, including challenging narrow-gap systems and spin-pure two-determinant states of singlet diradicals. This simple reformulation of the variational procedure can be readily extended to electron correlation methods with multiconfiguration states and to the optimization of excited-state orbitals.