Towards a Holomorphic Density Functional Theory.
Journal of chemical theory and computation
American Chemical Society
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Zarotiadis, R. A., Burton, H. G., & Thom, A. (2020). Towards a Holomorphic Density Functional Theory.. Journal of chemical theory and computation, 16 (12), 7400-7412. https://doi.org/10.1021/acs.jctc.0c00822
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.
Royal Society Cambridge Trusts
Royal Society (UF160398)
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External DOI: https://doi.org/10.1021/acs.jctc.0c00822
This record's URL: https://www.repository.cam.ac.uk/handle/1810/312949
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