Excitation energies along a range-separated adiabatic connection

TL;DR

This paper investigates how excitation energies vary along a range-separated adiabatic connection, demonstrating that intermediate interaction levels yield more accurate excitation energies, especially in strongly correlated systems, aiding the development of density-functional methods.

Contribution

It introduces a novel approach to study excitation energies along a range-separated adiabatic connection, highlighting the benefits of partial interactions for accurate excitation energy calculations.

Findings

Intermediate interaction points improve excitation energy accuracy.

Long-range interacting systems serve as better starting points.

Results are validated on He, Be, and H2 systems.

Abstract

We present a study of the variation of total energies and excitationenergies along a range-separated adiabatic connection. This connectionlinks the non-interacting Kohn-Sham electronic system to the physicalinteracting system by progressively switching on theelectron-electron interactions whilst simultaneously adjusting aone-electron effective potential so as to keep the ground-statedensity constant. The interactions are introduced in arange-dependent manner, first introducing predominantly long-range,and then all-range, interactions as the physical system is approached,as opposed to the conventional adiabatic connection where theinteractions are introduced by globally scaling the standard Coulomb interaction.Reference data are reported for the He and Be atoms and the H2molecule, obtained by calculating the short-range effective potentialat the full configuration-interaction level using Lieb'sLegendre-transform approach. As the strength of the electron-electroninteractions increases, the excitation energies, calculated for thepartially interacting systems along the adiabatic connection, offerincreasingly accurate approximations to the exact excitation energies.Importantly, the excitation energies calculated at an intermediatepoint of the adiabatic connection are much better approximations tothe exact excitation energies than are the corresponding Kohn-Shamexcitation energies. This is particularly evident in situationsinvolving strong static correlation effects and states with multipleexcitation character, such as the dissociating H2 molecule. Theseresults highlight the utility of long-range interacting referencesystems as a starting point for the calculation of excitation energiesand are of interest for developing and analyzing practical approximaterange-separated density-functional methodologies.