| Autor: |
Burgess AC; School of Physics, Trinity College Dublin, The University of Dublin, Ireland., Linscott E; Laboratory for Materials Simulations, Paul Scherrer Institut, 5232 Villigen PSI, Switzerland.; National Centre for Computational Design and Discovery of Novel Materials (MARVEL), Paul Scherrer Institut, 5232 Villigen PSI, Switzerland., O'Regan DD; School of Physics, Trinity College Dublin, The University of Dublin, Ireland. |
| Jazyk: |
angličtina |
| Zdroj: |
Physical review letters [Phys Rev Lett] 2024 Jul 12; Vol. 133 (2), pp. 026404. |
| DOI: |
10.1103/PhysRevLett.133.026404 |
| Abstrakt: |
The piecewise linearity condition on the total energy with respect to the total magnetization of finite quantum systems is derived using the infinite-separation-limit technique. This generalizes the well-known constancy condition, related to static correlation error, in approximate density functional theory. The magnetic analog of Koopmans' theorem in density functional theory is also derived. Moving to fractional electron count, the tilted-plane condition is derived, lifting certain assumptions in previous works. This generalization of the flat-plane condition characterizes the total energy surface of a finite system for all values of electron count N and magnetization M. This result is used in combination with tabulated spectroscopic data to show the flat-plane structure of the oxygen atom, among others. We find that derivative discontinuities with respect to electron count sometimes occur at noninteger values. A diverse set of tilted-plane structures is shown to occur in d-orbital subspaces, depending on chemical coordination. General occupancy-based total-energy expressions are demonstrated thereby to be necessarily dependent on the symmetry-imposed degeneracies. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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