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Discontinuities of Kinetic Energy Densities within Finite and Complete Basis Sets.

Conrad C MooreViktor N Staroverov
Published in: The journal of physical chemistry. A (2024)
Although electron densities are always continuous, other ingredients of density-functional approximations can be sharply discontinuous at isolated points. In particular, the positive-definite, Weizsäcker, and Pauli kinetic energy densities expressed in terms of Slater-type orbitals all have discontinuities at the positions of the atomic nuclei in molecules. The first two of those quantities are similarly discontinuous even in the basis-set limit. These striking features are not as widely recognized as they deserve to be. We show in detail how discontinuities of kinetic energy densities arise from asymmetric electron-nucleus cusps of molecular wave functions and point out instances of their significance in electronic structure theory.
Keyphrases
  • density functional theory
  • molecular dynamics