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The Pauli exclusion principle requires the spectrum of the occupation numbers of the one-electron reduced density matrix (1-RDM) to be bounded by one and zero. However, for a 1-RDM from a wave function, there exist additional conditions on…

Chemical Physics · Physics 2014-04-22 Romit Chakraborty , David A. Mazziotti

One-electron reduced density matrices (1RDMs) from equation-of-motion (EOM) coupled-cluster with single and double excitations (CCSD) calculations are analyzed to assess their N-representability ({\em i.e.}, whether they are derivable from…

Chemical Physics · Physics 2023-07-14 Stephen H. Yuwono , A. Eugene DePrince

We investigate the structure of the one-body Reduced Density Matrix (1RDM) of three electron systems, i.e. doublet and quadruplet spin configurations, corresponding to the smallest interacting system with an open-shell ground state. To this…

Chemical Physics · Physics 2018-03-22 Iris Theophilou , Nektarios Lathiotakis , Nicole Helbig

We consider necessary conditions for the one-body-reduced density matrix (1RDM) to correspond to a triplet wave-function of a two electron system. The conditions concern the occupation numbers and are different for the high spin…

Chemical Physics · Physics 2016-05-30 Iris Theophilou , Nektarios N. Lathiotakis , Nicole Helbig

We propose and work out a reduced density matrix functional theory (RDMFT) for calculating energies of eigenstates of interacting many-electron systems beyond the ground state. Various obstacles which historically have doomed such an…

Quantum Physics · Physics 2021-07-08 Christian Schilling , Stefano Pittalis

A crucial theorem in Reduced Density Matrix Functional Theory (RDMFT) suggests that the universal pure and ensemble functional coincide on their common domain of pure N-representable one-matrices. We refute this by a comprehensive analysis…

Quantum Physics · Physics 2018-12-24 Christian Schilling

We establish necessary and sufficient conditions for the N-representability of the universal one-electron reduced density matrix functional. Functionals satisfying these conditions are guaranteed to yield variational upper bounds on the…

Quantum Physics · Physics 2026-04-08 Jannis Erhard , Paul W. Ayers

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…

Quantum Physics · Physics 2024-08-20 Matthieu Vladaj , Quentin Marécat , Bruno Senjean , Matthieu Saubanère

Based on recent progress on fermionic exchange symmetry we propose a way to develop new functionals for reduced density matrix functional theory. For some settings with an odd number of electrons, by assuming saturation of the inequalities…

Strongly Correlated Electrons · Physics 2018-10-23 Carlos L. Benavides-Riveros , Miguel A. L. Marques

Lately, there has been a renewed interest in fermionic 1-body reduced density matrices and their restrictions beyond the Pauli principle. These restrictions are usually quantified using the polytope of allowed, ordered eigenvalues of such…

Quantum Physics · Physics 2024-06-19 Robin Reuvers

The $N$-representability problem places fundamental constraints on reduced density matrices (RDMs) that originate from physical many-fermion quantum states. Motivated by recent developments in functional theories, we introduce a hierarchy…

Quantum Physics · Physics 2026-04-28 Julia Liebert , Anna O. Schouten , Irma Avdic , Christian Schilling , David A. Mazziotti

We present a constructive solution to the N-representability problem---a full characterization of the conditions for constraining the two-electron reduced density matrix (2-RDM) to represent an N-electron density matrix. Previously known…

Quantum Physics · Physics 2012-07-04 David A. Mazziotti

As a new approach to efficiently describe correlation effects in the relativistic quantum world we propose to consider reduced density matrix functional theory, where the key quantity is the first-order reduced density matrix (1-RDM). In…

Chemical Physics · Physics 2022-05-05 M. Rodríguez-Mayorga , K. J. H. Giesbertz , L. Visscher

The exponential computational cost of describing strongly correlated electrons can be mitigated by adopting a reduced density-matrix (RDM)-based description of the electronic structure. While variational two-electron RDM (v2RDM) methods can…

Chemical Physics · Physics 2026-01-06 Grier M. Jones , Run. R. Li , A. Eugene DePrince , Konstantinos D. Vogiatzis

The direct variational optimization of the two-electron reduced density matrix (2RDM) can provide a reference-independent description of the electronic structure of many-electron systems that naturally captures strong or nondynamic…

Chemical Physics · Physics 2024-06-19 Run R. Li , Marcus D. Liebenthal , A. Eugene DePrince

From a geometric point of view, Pauli's exclusion principle defines a hypersimplex. This convex polytope describes the compatibility of $1$-fermion and $N$-fermion density matrices, therefore it coincides with the convex hull of the pure…

Minimizing the energy of an $N$-electron system as a functional of a two-electron reduced density matrix (2-RDM), constrained by necessary $N$-representability conditions (conditions for the 2-RDM to represent an ensemble $N$-electron…

Chemical Physics · Physics 2016-06-21 Nicholas C. Rubin , David A. Mazziotti

The variational two-electron reduced density matrix (v2RDM) method is generalized for the description of total angular momentum ($J$) and projection of total angular momentum ($M_{J}$) states in atomic systems described by non-relativistic…

Chemical Physics · Physics 2022-08-05 Run R. Li , Nicholas C. Rubin , A. Eugene DePrince

Variational minimization of the ground-state energy as a function of the two-electron reduced density matrix (2-RDM), constrained by necessary $N$-representability conditions, provides a polynomial-scaling approach to studying strongly…

Quantum Physics · Physics 2011-11-09 Kasra Naftchi-Ardebili , Nathania W. Hau , David A. Mazziotti

In many of the approximate functionals in one-body reduced density matrix (1RDM) functional theory, the approximate two-body reduced density matrix (2RDM) in the natural orbital representation only depends on the natural occupation numbers.…

Chemical Physics · Physics 2020-11-24 Klaas J. H. Giesbertz
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