Variational minimization scheme for the one-particle reduced density matrix functional theory in the ensemble N-representability domain
arxiv(2024)
摘要
The one-particle reduced density-matrix (1-RDM) functional theory is a
promising alternative to density-functional theory (DFT) that uses the 1-RDM
rather than the electronic density as a basic variable. However, long-standing
challenges such as the lack of Kohn–Sham scheme and the complexity of the pure
N-representability conditions are still impeding its wild utilization.
Fortunately, ensemble N-representability conditions derived in the natural
orbital basis are known and trivial, such that almost every functionals of the
1-RDM are actually natural orbital functionals which do not perform well for
all the correlation regimes. In this work, we propose a variational
minimization scheme in the ensemble N-representable domain that is not
restricted to the natural orbital representation of the 1-RDM. We show that
splitting the minimization into the diagonal and off-diagonal part of the 1-RDM
can open the way toward the development of functionals of the orbital
occupations, which remains a challenge for the generalization of
site-occupation functional theory in chemistry. Our approach is tested on the
uniform Hubbard model using the Müller and the Töws–Pastor functionals, as
well as on the dihydrogen molecule using the Müller functional.
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