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Physical Review A

Parametrization of the two-electron reduced density matrix for its direct calculation without the many-electron wave function: Generalizations and applications

David A. Mazziotti

Published Jun 30, 2010• 52 citations
Publisher

Abstract

An improved parametrization of the two-electron reduced density matrix (2-RDM) [D. A. Mazziotti, Phys. Rev. Lett. 101, 253002 (2008)] was recently shown to yield energies and properties that are markedly better than those calculated by traditional ab initio methods of similar computational scaling. In this paper a family of such energy functionals, generalizing the ones obtained previously, is derived through the use of (i) $p$-particle contraction relations based on the contraction of the cumulant expansions of $p$-particle RDMs and (ii) Cauchy-Schwarz relations that arise from an important set of $N$-representability constraints known as the two-positivity conditions. The 2-RDMs are explicitly parameterized in terms of the first-order part of the cumulant 2-RDM and, for the inclusion of single excitations, a second-order part of the 1-RDM. In contrast to earlier formulations based on the coefficients from configuration interaction with single and double excitations (CISD), the cumulant-based parametric 2-RDM methods, from the properties of cumulants, are rigorously size extensive. We also show that writing the energy functionals in terms of correlated 1-RDMs and cumulant 2-RDMs reduces the computational cost of the parametric 2-RDM methods to that of CISD. Applications are made to ground-state energies of several molecules, equilibrium bond distances, and frequencies of HF, ${\mathrm{F}}_{2}$, and CO, the relative energy of the cis and trans isomers of ${\mathrm{HO}}_{3}$${}^{\ensuremath{-}}$, and the HCN-HNC isomerization reaction. For bond breaking in hydrogen fluoride the improved and more efficient parametric 2-RDM methods yield energies with similar accuracies at both equilibrium and nonequilibrium geometries in 6-31G** and polarized valence quadruple-$\ensuremath{\zeta}$ basis sets. Computed 2-RDMs very nearly satisfy well-known $N$-representability conditions.

DOI
10.1103/physreva.81.062515

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An improved parametrization of the two-electron reduced density matrix (2-RDM) [D. A. Mazziotti, Phys. Rev. Lett. 101, 253002 (2008)] was recently shown to yield energies and properties that are markedly better than those calculated by traditional ab initio methods of similar computational scaling. In this paper a family of such energy functionals, generalizing the ones obtained previously, is derived through the use of (i) ppp-particle contraction relations based on the contraction of the cumulant expansions of ppp-particle RDMs and (ii) Cauchy-Schwarz relations that arise from an important set of NNN-representability constraints known as the two-positivity conditions. The 2-RDMs are explicitly parameterized in terms of the first-order part of the cumulant 2-RDM and, for the inclusion of single excitations, a second-order part of the 1-RDM. In contrast to earlier formulations based on the coefficients from configuration interaction with single and double excitations (CISD), the cumulant-based parametric 2-RDM methods, from the properties of cumulants, are rigorously size extensive. We also show that writing the energy functionals in terms of correlated 1-RDMs and cumulant 2-RDMs reduces the computational cost of the parametric 2-RDM methods to that of CISD. Applications are made to ground-state energies of several molecules, equilibrium bond distances, and frequencies of HF, F2{\mathrm{F}}_{2}F2​, and CO, the relative energy of the cis and trans isomers of {\mathrm{HO}}_{3}$${}^{\ensuremath{-}}, and the HCN-HNC isomerization reaction. For bond breaking in hydrogen fluoride the improved and more efficient parametric 2-RDM methods yield energies with similar accuracies at both equilibrium and nonequilibrium geometries in 6-31G** and polarized valence quadruple-\ensuremathζ\ensuremath{\zeta}\ensuremathζ basis sets. Computed 2-RDMs very nearly satisfy well-known NNN-representability conditions.
Parametrization of a molecular two-electron reduced density matrix (2-RDM) enables energies and properties to be directly computed at a highly efficient computational cost. In this Letter an improved 2-RDM parametrization yields energies and properties that are markedly better than those calculated with a similar computational scaling by traditional ab initio methods. Computed 2-RDMs very nearly satisfy well-known N-representability conditions. Applications are made to ground-state energies of several molecules and equilibrium bond distances and harmonic frequencies of HF, F2, and CO. The method for single-bond breaking in HF and CH4 yields similar accuracy at equilibrium and nonequilibrium geometries.
Correlation energies and reduced density matrices (RDMs) of atoms and molecules are directly computed by solving the 1,3-contracted Schr\"odinger equation (1,3-CSE). The solution of the 1,3-CSE synthesizes two optimization strategies recently employed for the direct determination of the 2-RDM: (i) variational minimization of the energy with respect to a 2-RDM constrained by positivity conditions [D. A. Mazziotti, Phys. Rev. A 65,65,65, 062511 (2002)] and (ii) the contracted power method for solving the 2,4-CSE [D. A. Mazziotti, J. Chem. Phys. 116,116,116, 1239 (2002)]. While both the 3- and the 4-RDMs in the 2,4-CSE are reconstructed from the 2-RDM by cumulant expansions, similar techniques cannot be directly applied to the 1,3-CSE because constructing the 2-RDM from the 1-RDM with cumulant theory does not improve upon the mean-field approximation. We, however, establish a unique mapping from the 1-RDM to the 2-RDM by searching for the 2-RDM, constrained by contraction and N-representability conditions, which minimizes the energy. The 2-RDM constrained search is practically implemented through recent advances in positive semidefinite programming. With the variational reconstruction of the 2-RDM and a cumulant reconstruction of the 3-RDM, the 1,3-CSE may be solved via a contracted power method for the ground-state energy and RDMs. The initial RDMs, it is shown, need not be N representable for the contracted power method to converge; this allows us to choose the original RDMs from a variational calculation with approximate N-representability conditions on the 2-RDM. Application of the 1,3-CSE algorithm to atoms and molecules yields highly accurate correlation energies both near and far from equilibrium geometries.
Molecular ground-state energies and two-electron reduced density matrices (2-RDMs) have recently been computed without the many-electron wave function by constraining the 2-RDM to satisfy a complete set of three-positivity conditions for N representability [D. A. Mazziotti, Phys. Rev. A 74, 032501 (2006)]. Energies at both equilibrium and nonequilibrium geometries are obtained within 0.3% of the correlation energy. In this paper the authors extend this work to examine the accuracy of molecular properties, including multipole moments and components of the ground-state energy, relative to full configuration interaction (FCI). Comparisons are also made with 2-RDM methods with two-positivity conditions and two-positivity plus the generalized T1T2 conditions as well as several approximate wave function methods. Using the 2-RDM method with three-positivity conditions, the authors obtain dipole, quadrupole, and octupole moments for BeH2, BH, H2O, CO, and NH3 at equilibrium geometries that are within 0.04% of their FCI values. In addition, for the potential energy surface of N2, the 2-RDM method with three-positivity yields not only accurate total ground-state energies but also accurate expectation values of the kinetic energy operator, the electron-nuclei potential, and electron-electron repulsion.
Treatment of two-electron excitations is a fundamental but computationally expensive part of ab initio calculations of many-electron correlation. In this paper we develop a low-rank spectral expansion of two-electron excitations for accelerated electronic-structure calculations. The spectral expansion differs from previous approaches by relying upon both (i) a sum of three expansions to increase the rank reduction of the tensor and (ii) a factorization of the tensor into geminal (rank-two) tensors rather than orbital (rank-one) tensors. We combine three spectral expansions from the three distinct forms of the two-electron reduced density matrix (2-RDM), (i) the two-particle (2)D, (ii) the two-hole (2)Q, and the (iii) particle-hole (2)G matrices, to produce a single spectral expansion with significantly accelerated convergence. While the resulting expansion is applicable to any quantum-chemistry calculation with two-particle excitation amplitudes, it is employed here in the parametric 2-RDM method [D. A. Mazziotti, Phys. Rev. Lett. 101, 253002 (2008)]. The low-rank parametric 2-RDM method scales quartically with the basis-set size, but like its full-rank version it can capture multi-reference correlation effects that are difficult to treat efficiently by traditional single-reference wavefunction methods. Applications are made to computing potential energy curves of HF and triplet OH(+), equilibrium bond distances and frequencies, the HCN-HNC isomerization, and the energies of hydrocarbon chains. Computed 2-RDMs nearly satisfy necessary N-representability conditions. The low-rank spectral expansion has the potential to expand the applicability of the parametric 2-RDM method as well as other ab initio methods to large-scale molecular systems that are often only treatable by mean-field or density functional theories.
Molecular two-electron reduced density matrices (2-RDMs) are computed variationally without the many-electron wave function by constraining the 2-RDM with a set of three-particle NNN-representability conditions known as three-positivity conditions. These constraints restrict four distinct three-particle probability distributions, which can be defined for any NNN-particle system, to be nonnegative. The variational calculation of the 2-RDM with full three-positivity conditions is implemented with the first-order semidefinite programming algorithm [D.A. Mazziotti, Phys. Rev. Lett. 93, 213001 (2004)]. We also derive and implement a generalization of the T2{T}_{2}T2​ representability condition, which is a subset of the three-positivity conditions. Energies and 2-RDMs are computed for several molecules as well as the nitrogen molecule at both equilibrium and nonequilibrium geometries. The ground-state energies for nitrogen are within 0.0015a.u.0.0015\phantom{\rule{0.3em}{0ex}}\mathrm{a.u.}0.0015a.u. of the values from full configuration interaction at all internuclear distances.
Two-electron reduced density matrices (2-RDMs) of many-electron molecules are directly determined without calculation of their wave functions by solving the anti-Hermitian contracted Schrödinger equation. Approximation of the 3-RDM in the anti-Hermitian contracted Schrödinger equation by a corrected cumulant expansion [Mazziotti, Phys. Rev. A 60, 3618 (1999)] permits the direct calculation of the energy and 2-RDM with many high-order correlation effects included. The method is illustrated for the molecules BeH2, H2O, NH3, CH4, and CO as well as the dissociation of BH. Correlation energies are obtained within 95%-100% of full-configuration interaction, and 2-RDMs very nearly satisfy known N-representability conditions.