| Autor: |
Zarotiadis, Rhiannon A., Burton, Hugh G. A., Thom, Alex J. W. |
| Rok vydání: |
2020 |
| Předmět: |
|
| Zdroj: |
J. Chem. Theory Comput. 2020, 16, 12, 7400-7412 |
| Druh dokumentu: |
Working Paper |
| DOI: |
10.1021/acs.jctc.0c00822 |
| Popis: |
Self-consistent-field (SCF) approximations formulated using Hartree-Fock (HF) or Kohn-Sham Density Functional Theory (KS-DFT) both have the potential to yield multiple solutions. However, the formal relationship between multiple solutions identified using HF or KS-DFT remains generally unknown. We investigate the connection between multiple SCF solutions for HF or KS-DFT by introducing a parametrised functional that scales between the two representations. Using the hydrogen molecule and a model of electron transfer, we continuously map multiple solutions from the HF potential to a KS-DFT description. We discover that multiple solutions can coalesce and vanish as the functional changes, forming a direct analogy with the disappearance of real HF solutions along a change in molecular structure. To overcome this disappearance of solutions, we develop a complex-analytic extension of DFT - the "holomorphic DFT" approach - that allows every SCF stationary state to be analytically continued across all molecular structures and exchange-correlation functionals. |
| Databáze: |
arXiv |
| Externí odkaz: |
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