Dispersion with Fixed Diagonal Matrices: Exchange energy correction and an assessment of the Becke-Roussel exchange hole (2401.02125v1)

Abstract: An exchange-correction to the Fixed Diagonal Matrices (FDM) method is introduced to improve accuracy when employing a single reference wavefunction. Also, the performance of the Becke-Roussel exchange-hole for approximating the pair density mediated integrals is explored. With the exchange-correction, the FDM procedure yields dispersion coefficients for closed-shell atoms on par with highly correlated methods when using Hartree-Fock or Kohn-Sham pair density. Conversely, the Becke-Roussel exchange-hole results in an overestimation of the dispersion coefficients for closed-shell atoms. In general, the FDM method fails in underestimating the dispersion coefficients of open-shell atoms and ions.