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Chemical Physics Letters

Extraction of ionization energies from the ground-state two-particle reduced density matrix

John D. Farnum, David A. Mazziotti

Published Nov 12, 2004• 16 citations
Publisher
DOI
10.1016/j.cplett.2004.10.075

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Electronic excited states are computed through a technique for extracting them from a knowledge of the ground-state two-particle reduced density matrix (2-RDM). Diagonalization of the Hamiltonian in the basis set of one-particle excitations, deexcitations, and projections from the ground-state wave function yields those excited states dominated by one-particle excitations; however, explicit evaluation of the Hamiltonian requires a knowledge of the ground-state 4-RDM. Two techniques are developed for evaluating the Hamiltonian elements with only a knowledge of the 2-RDM: (i) the cumulant method in which the higher RDMs are reconstructed from the 2-RDM via cumulant theory and (ii) the Hermitian or anti-Hermitian operator method in which the higher RDMs are eliminated by selecting the basis functions to be Hermitian or anti-Hermitian. These techniques are extendable to the diagonalization of the Hamiltonian in basis sets of m-excitations where m>1.m>1.m>1. Excited-state energies with an accuracy between 0.1% and 0.001% of their absolute values are determined in illustrative calculations on Be, LiH, H2O,{\mathrm{H}}_{2}\mathrm{O},H2​O, and BH.
In most nuclear many-body methods, observables are calculated using many-body wave functions explicitly. The variational two-particle reduced density matrix method is one of the few exceptions to the rule. Ground-state energies of both closed-shell and open-shell nuclear systems can indeed be evaluated by minimizing a constrained linear functional of the two-particle reduced density matrix. However, it has virtually never been used in nuclear theory, because nuclear ground states were found to be well overbound, contrary to those of atoms and molecules. Consequently, we introduced new constraints in the nuclear variational two-particle reduced density matrix method, developed recently for atomic and molecular systems. Our calculations then show that this approach can provide a proper description of nuclear systems where only valence neutrons are included. For the nuclear systems where both neutrons and protons are active, however, the energies obtained with the variational two-particle reduced density matrix method are still overbound. The possible reasons for the noticed discrepancies and solutions to this problem will be discussed.
Ground-state two-particle reduced density matrices (2-RDMs) are used to calculate excited-state energy spectra. Solving the Schrodinger equation for excited states dominated by single excitations from the ground-state wavefunction requires the ground-state 2- and 3-RDMs. The excited states, however, can be obtained without a knowledge of the ground-state 3-RDM by two methods: (i) cumulant expansion methods which build the 3-RDM from the 2-RDM, and (ii) double commutator methods which eliminate the 3-RDM. Previous work [Mazziotti, Phys. Rev. A 68, 052501 (2003)] examined the accuracy of excited states extracted from ground-state 2-RDMs, which were calculated by full configuration interaction or the variational 2-RDM method. In this work we employ (i) advances in semidefinite programming to treat the excited states of water and hydrogen fluoride and chains of hydrogen atoms, and (ii) the addition of partial three-particle N-representability conditions to compute more accurate ground-state 2-RDMs. With the hydrogen chains we examine the metal-to-insulator transition as measured by the band gap (the difference between the ground-state and the first excited-state energies), which is difficult for excited-state methods to capture.