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The Journal of Chemical Physics

Exact and approximate adiabatic connection formulae for the correlation energy in multireference ground and excited states

Katarzyna Pernal

Published Nov 26, 2018• 33 citations
Publisher

Abstract

Recently it has been shown how to employ the adiabatic connection (AC) formalism to obtain correlation energy for multireference wavefunctions [K. Pernal, Phys. Rev. Lett. 120, 013001 (2018)]. Approximations to the exact AC formulation have been based on assuming that a one-electron reduced density matrix is constant along the AC path and by employing the extended random phase approximation. In this paper, the importance of these approximations is examined by comparing approximate AC integrands with their exact counterparts obtained for the hydrogen molecule in its ground and excited states. Encouraging results obtained for H2 indicate that AC is a viable and promising approach to a correlation energy problem not only for ground but also for excited states of electronic systems.

DOI
10.1063/1.5048988

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Recently it has been shown how to employ the adiabatic connection (AC) formalism to obtain correlation energy for multireference wavefunctions [K. Pernal, Phys. Rev. Lett. 120, 013001 (2018)]. Approximations to the exact AC formulation have been based on assuming that a one-electron reduced density matrix is constant along the AC path and by employing the extended random phase approximation. In this paper, the importance of these approximations is examined by comparing approximate AC integrands with their exact counterparts obtained for the hydrogen molecule in its ground and excited states. Encouraging results obtained for H2 indicate that AC is a viable and promising approach to a correlation energy problem not only for ground but also for excited states of electronic systems.
An adiabatic connection (AC) formula for the electron correlation energy is derived for a broad class of multireference wave functions. The AC expression recovers dynamic correlation energy and assures a balanced treatment of the correlation energy. Coupling the AC formalism with the extended random phase approximation allows one to find the correlation energy only from reference one- and two-electron reduced density matrices. If the generalized valence bond perfect pairing model is employed a simple closed-form expression for the approximate AC formula is obtained. This results in the overall M^{5} scaling of the computation cost making the method one of the most efficient multireference approaches accounting for dynamic electron correlation also for the strongly correlated systems.
A multiconfigurational adiabatic connection (AC) formalism is an attractive approach to compute the dynamic correlation within the complete active space self-consistent field and density matrix renormalization group (DMRG) models. Practical realizations of AC have been based on two approximations: (i) fixing one- and two-electron reduced density matrices (1- and 2-RDMs) at the zero-coupling constant limit and (ii) extended random phase approximation (ERPA). This work investigates the effect of removing the "fixed-RDM" approximation in AC. The analysis is carried out for two electronic Hamiltonian partitionings: the group product function- and the Dyall Hamiltonians. Exact reference AC integrands are generated from the DMRG full configuration interaction solver. Two AC models are investigated, employing either exact 1- and 2-RDMs or their second-order expansions in the coupling constant in the ERPA equations. Calculations for model molecules indicate that lifting the fixed-RDM approximation is a viable way toward improving the accuracy of existing AC approximations.
An adiabatic connection (AC) is developed as an electron correlation correction for doubly occupied configuration interaction (DOCI) wave functions. Following the work of Pernal [Phys. Rev. Lett. 120, 013001 (2018)], the working equations of the approach, termed AC-DOCI, are rooted in the extended random phase approximation (ERPA) and require knowledge of only the ground-state two-electron reduced density matrix (2RDM) from the DOCI. As such, the AC is naturally suited to modeling electron correlation in variational 2RDM (v2RDM)-based approximations to the DOCI. The v2RDM-driven AC-DOCI is applied to the dissociation of molecular nitrogen and the double dissociation of water; the approach yields energies that are similar in quality to those from second-order multireference perturbation theory near equilibrium, but the quality of the AC-DOCI energy degrades at stretched geometries. The exact adiabatic connection path suggests the assumption that the one-electron reduced-density matrix is constant along the AC path is invalid at stretched geometries, but this deficiency alone cannot explain the observed behavior. Rather, it appears that the ERPA's single-particle-transition ansatz cannot, in general, provide good approximations to the 2RDM along the AC path. The AC-DOCI is also applied to a set of 45 reaction energies; for these systems, the approach has an average accuracy that is comparable to that of single-reference second-order many-body perturbation theory.
The connection between the adiabatic excitation energy of time-dependent density functional theory and the ground state correlation energy from the adiabatic connection fluctuation-dissipation theorem (ACFDT) is explored in the limiting case of one excited state. An exact expression is derived for any adiabatic Hartree-exchange-correlation kernel that connects the excitation energy and the potential contribution to correlation. The resulting formula is applied to the asymmetric Hubbard dimer, a system where this limit is exact. Results from a hierarchy of approximations to the kernel, including the random phase approximation (RPA) with and without exchange and the adiabatically exact (AE) approximation, are compared to the exact ones. At full coupling, the numerical results indicate a tension between predicting an accurate excitation energy and an accurate potential contribution to correlation. The AE approximation is capable of making accurate predictions of both quantities, but only in parts of the parameter space that classify as weakly correlated, while RPA tends to be unable to accurately predict these properties simultaneously anywhere. For a strongly correlated dimer, the AE approximation greatly overestimates the excitation energy yet continues to yield an accurate ground state correlation energy due to its accurate prediction of the adiabatic connection integrand. If similar trends hold for real systems, the development of correlation kernels will be important for applications of the ACFDT in systems with large potential contributions to correlation.
Currently, there is a growing interest in the development of a new hierarchy of methods based on the concept of seniority, which has been introduced quite recently in quantum chemistry. Despite the enormous potential of these methods, the accurate description of both dynamical and static correlation effects within a single and in-principle-exact approach remains a challenge. In this work, we propose an alternative formulation of reduced density-matrix functional theory (RDMFT) where the (one-electron reduced) density matrix is mapped onto an ab initio seniority-zero wave function. In this theory, the exact natural orbitals and their occupancies are determined self-consistently from an effective seniority-zero calculation. The latter involves a universal higher seniority density matrix functional for which an adiabatic connection (AC) formula is derived and implemented under specific constraints that are related to the density matrix. The pronounced curvature of the (constrained) AC integrand, which is numerically observed in prototypical hydrogen chains and the helium dimer, indicates that a description of higher seniority correlations within second-order perturbation theory is inadequate in this context. Applying multiple linear interpolations along the AC or connecting second-order perturbation theory to a full-seniority treatment via Pad\'e approximants are better strategies. Such information is expected to serve as a guide in the future design of higher seniority density-matrix functional approximations.
The quantum chemical version of the density matrix renormalization group (DMRG) method has established itself as one of the methods of choice for calculations of strongly correlated molecular systems. Despite its great ability to capture strong electronic correlation in large active spaces, it is not suitable for computations of dynamical electron correlation. In this work, we present a new approach to the electronic structure problem of strongly correlated molecules, in which DMRG is responsible for a proper description of the strong correlation, whereas dynamical correlation is computed via the recently developed adiabatic connection (AC) technique which requires only up to two-body active space reduced density matrices. We report the encouraging results of this approach on typical candidates for DMRG computations, namely, n -acenes ( n = 2 → 7), Fe(II)–porphyrin, and the Fe 3 S 4 cluster.