Robust ΔSCF calculations with direct energy functional minimization methods and STEP for molecules and materials

Abstract

The direct energy functional minimization method using the orbital transformation (OT) scheme in the program package CP2K has been employed for Δ self-consistent field (ΔSCF) calculations. The OT method for non-uniform molecular orbitals occupations allows us to apply the ΔSCF method for various kinds of molecules and periodic systems. Vertical excitation energies of heteroaromatic molecules and condensed phase systems, such as solvated ethylene and solvated uracil obeying periodic boundary conditions, are reported using the ΔSCF method. In addition, a Re–phosphate molecule attached to the surface of anatase (TiO2) has been investigated. Additionally, we have implemented a recently proposed state-targeted energy projection ΔSCF algorithm [K. Carter-Fenk and J. M. Herbert, J. Chem. Theory Comput. 16(8), 5067–5082 (2020)] for diagonalization based SCF in CP2K. It is found that the OT scheme provides a smooth and robust SCF convergence for all investigated excitation energies and (non-)periodic systems.