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Revisiting Artifacts of Kohn-Sham Density Functionals for Biosimulation by Slattery, Samuel A.; Yon, Jaden C.; Valeev, Edward F. is a scholarly article available to read on EtoBox.

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We revisit the problem of unphysical charge density delocalization/fractionalization induced by the self-interaction error of common approximate Kohn-Sham Density Functional Theory functionals on simulation of small to medium-size proteins in vacuum. Aside from producing unphysical electron densities and total energies, the vanishing of the HOMO-LUMO gap associated with the unphysical charge delocalization leads to an unphysical low-energy spectrum and catastrophic failure of most popular solvers for the Kohn-Sham (KS) self-consistent field (SCF) problem. We apply a robust quasi-Newton SCF solver [Phys. Chem. Chem. Phys. 26, 6557 (2024)] to obtain solutions for some of these difficult cases. The anatomy of the charge delocalization is revealed by the natural deformation orbitals obtained from the density matrix difference between the Hartree-Fock and KS solutions; the charge delocalization can occur not only between charged fragments (such as in zwitterionic polypeptides) but also may involve neutral fragments. The vanishing-gap phenomenon and troublesome SCF convergence are both attributed to the unphysical KS Fock operator eigenspectra of molecular fragments (e.g., amino acids or

Author

Slattery, Samuel A.; Yon, Jaden C.; Valeev, Edward F.

Published

2024

Language

EN