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Physical Review A

Necessary conditions for the N -representability of the second-order reduced density matrix: Upper bounds on the P and Q matrices

Dimitri Van Neck, Paul W. Ayers

Published Mar 5, 2007• 13 citations
Publisher

Abstract

Usually, variational calculations for the second-order reduced density matrix are performed subject to the constraint that the ``$P$'' and ``$Q$'' matrices are positive semidefinite, which only constrains the lowest eigenvalue of these matrices. We characterize the highest eigenvalue of these matrices and discuss how the associated constraint (which is related to the ground-state energy of the Hamiltonians $H=\ensuremath{-}P$ and $H=\ensuremath{-}Q$) can be implemented in practical calculations. This necessary condition for $N$-representability should help ensure that the second-order reduced density matrix is not ``overcorrelated.''

DOI
10.1103/physreva.75.032502

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Usually, variational calculations for the second-order reduced density matrix are performed subject to the constraint that the $P$'' and QQQ'' matrices are positive semidefinite, which only constrains the lowest eigenvalue of these matrices. We characterize the highest eigenvalue of these matrices and discuss how the associated constraint (which is related to the ground-state energy of the Hamiltonians H=\ensuremath−PH=\ensuremath{-}PH=\ensuremath−P and H=\ensuremath−QH=\ensuremath{-}QH=\ensuremath−Q) can be implemented in practical calculations. This necessary condition for NNN-representability should help ensure that the second-order reduced density matrix is not ``overcorrelated.''
In this work, we analyze the effectiveness of different sets of well-known necessary N-representability conditions that are imposed on the variational determination of two-electron reduced density matrices corresponding to the ground and excited states of N-electron Hamiltonians within doubly occupied configuration interaction subspaces. The two-electron reduced density matrix elements are determined so that they are suitably related to those of higher-order reduced density matrices and other associated matrices, up to a given order, constituting positive semidefinite matrices. These conditions up to two-, three-, and four-order have been sequentially imposed on the variational calculation of the expectation values of the dispersion operator corresponding to several Hamiltonian models, obtaining the electronic spectra. These results have been contrasted with those arising from the full configuration interaction method, illuminating the sufficiency/insufficiency of the variational N-representability conditions applied.
The expectation value of the Hamiltonian H for a many-electron system may be expressed in terms of the reduced second-order density matrix and the “reduced” Hamiltonian K for a two-electron system. It may be shown that the antisymmetric component HAS of the original Hamiltonian is an “outer projection” of K with respect to the antisymmetrizer O, so that HAS = OKO. This result implies that the eigenvalues of K are, in order, lower bounds to the eigenvalues of HAS, i.e. to the eigenvalues of H associated with the antisymmetry requirement. The expectation values of K are hence often below the ground state energy of H, and the eigenvalues may be used for the calculation of lower bounds. Some numerical applications to atoms serve as an illustration, and it is shown that the lower bounds become worse as the number of electrons increases. The implications for the “representability problem” are discussed.
Variational minimization of the ground-state energy as a function of the two-electron reduced density matrix (2-RDM), constrained by necessary NNN-representability conditions, provides a polynomial-scaling approach to studying strongly correlated molecules without computing the many-electron wave function. Here we introduce a route to enhancing necessary conditions for NNN representability through rank restriction of the 2-RDM. Rather than adding computationally more expensive NNN-representability conditions, we directly enhance the accuracy of two-particle (2-positivity) conditions through rank restriction, which removes degrees of freedom in the 2-RDM that are not sufficiently constrained. We select the rank of the particle-hole 2-RDM by deriving the ranks associated with model wave functions, including both mean-field and antisymmetrized geminal power (AGP) wave functions. Because the 2-positivity conditions are exact for quantum systems with AGP ground states, the rank of the particle-hole 2-RDM from the AGP ansatz provides a minimum for its value in variational 2-RDM calculations of general quantum systems. To implement the rank-restricted conditions, we extend a first-order algorithm for large-scale semidefinite programming. The rank-restricted conditions significantly improve the accuracy of the energies; for example, the percentages of correlation energies recovered for HF, CO, and N2{}_{2}2​ improve from 115.2%, 121.7%, and 121.5% without rank restriction to 97.8%, 101.1%, and 100.0% with rank restriction. Similar results are found at both equilibrium and nonequilibrium geometries. While more accurate, the rank-restricted NNN-representability conditions are less expensive computationally than the full-rank conditions.
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 true energy in one-electron reduced density matrix functional theory, regardless of the strength of the interparticle repulsion. Conversely, any functional violating these conditions will necessarily underestimate the true energy for certain systems. These exact constraints impose a stringent restriction on density matrix functional approximations, as many existing functionals-including the Hartree-Fock functional-appear to violate them. This mathematical formalism, therefore, can guide the development of new approximate functionals and numerical algorithms.
The ground-state fermion second-order reduced density matrix (2-RDM) is determined variationally using itself as a basic variable. As necessary conditions of the N-representability, we used the positive semidefiniteness conditions, P, Q, and G conditions that are described in terms of the 2-RDM. The variational calculations are performed by using recently developed semidefinite programming algorithm (SDPA). The calculated energies of various closed- and open-shell atoms and molecules are excellent, overshooting only slightly the full-CI energies. There was no case where convergence was not achieved. The calculated properties also reproduce well the full-CI results.