Velocity Gauge for Oscillator Strength in $\Delta$SCF theory

TL;DR

This paper introduces a velocity gauge approach within $\Delta$SCF theory to accurately compute oscillator strengths, overcoming non-orthogonality issues and providing origin-independent results for electronic excitations.

Contribution

The study demonstrates that the velocity gauge naturally addresses non-orthogonality in $\Delta$SCF wavefunctions, improving oscillator strength predictions without additional corrections.

Findings

Velocity gauge yields origin-independent oscillator strengths.

Velocity gauge results are comparable to length-gauge with orthogonalization.

Using spin-purified singlet excitation enhances velocity gauge performance.

Abstract

Delta self-consistent-field ($\Delta$SCF) theory is widely used for electronic excitation energy calculations. However, calculating the corresponding oscillator strengths is challenging. The corresponding many-electron wavefunctions are not directly accessible. Both the ground-state and the excited-state wave functions from $\Delta$SCF are described by reference Kohn-Sham (KS) single-determinant wavefunctions for the fictitious non-interacting systems. The non-orthogonality between the ground and excited Kohn-Sham determinants from two different SCF calculations leads to unphysically origin-dependent transition properties, such as transition dipole moment and length-gauge oscillator strength. Including nuclei contribution in the perturbation is theoretically rigorous, but its effectiveness is only limited to neutral systems, as we show theoretically and numerically. While several other practical approaches have been proposed to tackle the non-orthogonality problem and yield reasonable results, inevitably the determinant of the ground state or the excited state is changed, as well as the density matrix. In this work, we explore the use of the velocity gauge to compute oscillator strength within $\Delta$SCF theory. We demonstrate that the velocity gauge is capable of naturally accounting for the non-orthogonality of $\Delta$SCF KS wavefunctions and offering origin-independent predictions without any additional correction schemes to the KS wavefunctions. Compared to the length-gauge results obtained via symmetric orthogonalization, velocity gauge can offer comparable results. Furthermore, the adoption of spin-purified singlet excitation energy in the velocity-gauge transition dipole moment significantly enhances the overall performance of the velocity gauge for $\Delta$SCF oscillator strength predictions on conjugated chromophores.