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arXiv:2210.16289 · The Journal of Physical Chemistry Letters

Projection-Based Density Matrix Renormalization Group in Density Functional Theory Embedding

Pavel Beran, Katarzyna Pernal, Fabijan Pavošević, Libor Veis

Published Jan 17, 2023• 8 citations
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Abstract

The density matrix renormalization group (DMRG) method has already proved itself as a very efficient and accurate computational method, which can treat large active spaces and capture the major part of strong correlation. Its application on larger molecules is, however, limited by its own computational scaling as well as demands of methods for treatment of the missing dynamical electron correlation. In this work, we present the first step in the direction of combining DMRG with density functional theory (DFT), one of the most employed quantum chemical methods with favorable scaling, by means of the projection-based wave function (WF)-in-DFT embedding. On two proof-of-concept but important molecular examples, we demonstrate that the developed DMRG-in-DFT approach provides a very accurate description of molecules with a strongly correlated fragment.

DOI
10.1021/acs.jpclett.2c03298

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The density matrix renormalization group (DMRG) method has already proved itself as a very efficient and accurate computational method, which can treat large active spaces and capture the major part of strong correlation. Its application on larger molecules is, however, limited by its own computational scaling as well as demands of methods for treatment of the missing dynamical electron correlation. In this work, we present the first step in the direction of combining DMRG with density functional theory (DFT), one of the most employed quantum chemical methods with favorable scaling, by means of the projection-based wave function (WF)-in-DFT embedding. On two proof-of-concept but important molecular examples, we demonstrate that the developed DMRG-in-DFT approach provides a very accurate description of molecules with a strongly correlated fragment.
The projection-based wave function in density functional theory (WF-in-DFT) embedding enables an efficient description of both the energetics and properties of large and complex chemical systems, with accuracy exceeding that of pure DFT. Recently, we have proposed using the density matrix renormalization group (DMRG) as the WF method for molecules containing strongly correlated fragments [ Beran, P. J. Phys. Chem. Lett. 2023, 14, 716–722]. In this work, we demonstrate that the accuracy of the DMRG-in-DFT approach is primarily limited by the approximate treatment of the coupling between the active component and its environment through nonadditive exchange-correlation functionals. To address this issue, we combine exact exchange to reduce the nonadditive exchange error with a multireference adiabatic connection (AC) scheme to recover nonadditive correlation. The performance of the improved DMRG-in-DFT embedding is illustrated on two prototypical strongly correlated systems: the dissociation of the H 20 chain and the cleavage of a triple CN bond in propionitrile.
The projection-based wave function (WF)-in-DFT embedding enables an efficient description of both the energetics and properties of large and complex chemical systems, with accuracy exceeding that of pure DFT. Recently, we have proposed using the density matrix renormalization group (DMRG) as the WF method for molecules containing strongly correlated fragments [Beran, P. et al. J. Phys. Chem. Lett. 2023, 14, 3, 716-722]. In this work, we demonstrate that the accuracy of the DMRG-in-DFT approach is primarily limited by the approximate treatment of the coupling between the active component and its environment through nonadditive exchange-correlation functionals. To address this issue, we combine exact exchange to reduce the nonadditive exchange error with a multireference adiabatic connection (AC) scheme to recover nonadditive correlation. The performance of the improved DMRG-in-DFT embedding is illustrated on two prototypical strongly correlated systems: the dissociation of the H20 chain and the cleavage of a triple CN bond in propionitrile.
The ab initio density matrix renormalization group (DMRG) method has been well-established and has become one of the most accurate numerical methods for the precise electronic structure solution of large active spaces. In the past few years, to capture the missing dynamic correlation, various post-DMRG approaches have been proposed through the combination of DMRG and multireference quantum chemical methods or density functional theory. With this in mind, this work provides a brief overview of ab initio DMRG principles and the new developments within post-DMRG methods. For clarity, post-DMRG methods are classified into two main categories depending on whether high-order n -electron reduced density matrices are used, and their merits and disadvantages are properly discussed. Finally, we conclude by discussing unsolved bottlenecks and giving development perspectives of post-DMRG approaches, which are expected to yield quantitative descriptions of complex electronic structures in large strongly correlated molecules and materials.
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.
An implementation of the single-site density matrix renormalization group (DMRG) approach for the quantum-chemical application to calculate approximate as well as exact electronic ground-state energies and wave functions of atoms and molecules is presented.The algorithm is formulated in terms of the variational and sizeconsistent class of wave functions, matrix product states, and their operator analogues, matrix product operators.A procedure to construct quantum-chemical Hamiltonian operators with long-range Coulomb interactions as matrix product operators is developed.The many-electron Hamiltonian operators are represented as sums and products of one-electron operators.For the efficient matrix product operator construction of quantum-chemical Hamiltonians, different basis spaces including discrete position and momentum space as well as molecular and atomic orbitals are investigated.Discrete position space yields the best matrix product operator size scaling, but introduces artificial long-range couplings in the kinetic energy term of the Hamiltonian which are a consequence of the DMRG algorithm in terms of matrix product states.The huge amount of discrete space points needed for an accurate description poses a problem because of the electron-electron interaction.Therefore, a momentum space or Fourier series expansion of the electron-electron interaction is shown which makes it possible to compress its matrix product operator representation.DMRG applied to quantum-chemical Hamiltonians in matrix product operator form can serve as means to directly (without mean-field treatment in advance) investigate quantum-chemical problems and find the analytically exact ground-state solution of small atoms and molecules.The next basis space analyzed in detail is the atomic orbital basis.The matrix product operator construction and the direct application of the DMRG method in this basis is examined.A physical compression scheme based on a singular value decomposition of the electron-electron interaction in the atomic orbital basis is demonstrated.Furthermore, DMRG calculations in the atomic orbital basis for certain systems where mean-field theory yields qualitatively wrong results and where higher-order approximative correction methods like truncated configuration interaction and coupled cluster cannot fully capture strong electron correlation effects are compared to results obtained in the molecular orbital basis.The comparison shows that atomic orbitals describe the physical situation well and thus lead to a tremendous reduction of the matrix product state dimension and the computational effort.i
A major challenge in molecular electronic structure theory arises from chemical systems where the mean-field picture based upon a single electronic configuration fails to properly describe mechanics of many electrons. Such complex electronic states should be accounted for using a correlated superposition of multiple determinants and are referred to as multireference in quantum chemistry. Application domain of traditional multireference methods is severely limited to systems containing a small number of correlated electrons because of their exponential complexity. In recent years, much attention has been drawn to the density matrix renormalization group (DMRG) theory as a promising alternative. It has been introduced in ab initio quantum chemistry calculations and shown to be a highly-scalable multireference method that can handle full quantum degrees of freedom for the strongly-correlated wavefunction with unprecedented large configuration space. In this article, we provide an explicative introduction to the underlying theory and formalism built into the DMRG method and give a brief overview of our methodological extensions that combine DMRG and active-space correlation models.