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Journal of Chemical Theory and Computation

Quantum Chemistry Density Matrix Renormalization Group in the Discrete Variable Representation

Bing Gu, Jiajun Ren, Junzhe Zhang

Published Jul 2, 2025• 0 citations
Publisher

Abstract

We present a numerical implementation of the quantum chemistry density matrix renormalization group (DMRG) using the hybrid discrete variable representation (DVR)/Gaussian basis set. The z -axis of real space is discretized by a DVR basis set and each transversal plane is described by the eigenstates of the transversal core Hamiltonian, represented in a set of primitive Gaussian basis functions. Such a hybrid basis can reduce the computation of two-electron repulsion integrals. One main advantage of using the local DVR basis sets over finite-difference methods for real space discretization is that the kinetic energy operator matrix elements can be computed exactly. This method is first applied to a one-dimensional pseudo-hydrogen chain under screened Coulomb potential and then to a realistic hydrogen chain, whereby the DMRG/DVR results are comparable in accuracy to the full configuration interaction results.

DOI
10.1021/acs.jctc.5c00029

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We present a numerical implementation of the quantum chemistry density matrix renormalization group (DMRG) using the hybrid discrete variable representation (DVR)/Gaussian basis set. The z -axis of real space is discretized by a DVR basis set and each transversal plane is described by the eigenstates of the transversal core Hamiltonian, represented in a set of primitive Gaussian basis functions. Such a hybrid basis can reduce the computation of two-electron repulsion integrals. One main advantage of using the local DVR basis sets over finite-difference methods for real space discretization is that the kinetic energy operator matrix elements can be computed exactly. This method is first applied to a one-dimensional pseudo-hydrogen chain under screened Coulomb potential and then to a realistic hydrogen chain, whereby the DMRG/DVR results are comparable in accuracy to the full configuration interaction results.
We present a numerical implementation of the density matrix renormalization group (DMRG) using the discrete variable representation (DVR) basis set. One main advantage of using the local DVR basis sets is that the computations of one-electron integral and two-electron repulsion integrals are drastically simplified. For comparison, we further implemented DVR complete active space configuration interaction (CASCI) using canonical molecular orbitals. These methods are applied to a one-dimensional pseudo-hydrogen chain under screened Coulomb potential. The DMRG ground state energy agrees with CASCI up to 0.1 mEh with a very small number of bond dimensions.
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
We introduce a hybrid approach to applying the density matrix renormalization group to continuous systems, combining a grid approximation along one direction with a finite Gaussian basis set for the remaining two directions. This approach is especially useful for chainlike molecules, where the grid is used in the long direction. For hydrogen chain systems, the computational time scales approximately linearly with the number of atoms, as we show with near-exact minimal basis set calculations with up to 1000 atoms. The linear scaling comes from both the localization of the basis and a compression method for the long-ranged two-electron interaction. For shorter hydrogen chains, we show results with up to triple-ζ bases.
This article presents an efficient and parallelized implementation of the density matrix renormalization group (DMRG) algorithm for quantum chemistry calculations. The DMRG method as a large-scale multireference electronic structure model is by nature particularly efficient for one-dimensionally correlated systems, while the present development is oriented toward applications for polynuclear transition metal compounds, in which the macroscopic one-dimensional structure of electron correlation is absent. A straightforward extension of the DMRG algorithm is proposed with further improvements and aggressive optimizations to allow its application with large multireference active space, which is often demanded for metal compound calculations. Special efficiency is achieved by making better use of sparsity and symmetry in the operator and wave function representations. By accomplishing computationally intensive DMRG calculations, the authors have found that a large number of renormalized basis states are required to represent high entanglement of the electron correlation for metal compound applications, and it is crucial to adopt auxiliary perturbative correction to the projected density matrix during the DMRG sweep optimization in order to attain proper convergence to the solution. Potential energy curve calculations for the Cr(2) molecule near the known equilibrium precisely predicted the full configuration interaction energies with a correlation space of 24 electrons in 30 orbitals [denoted by (24e,30o)]. The energies are demonstrated to be accurate to 0.6mE(h) (the error from the extrapolated best value) when as many as 10,000 renormalized basis states are employed for the left and right DMRG block representations. The relative energy curves for [Cu(2)O(2)](2+) along the isomerization coordinate were obtained from DMRG and other correlated calculations, for which a fairly large orbital space (32e,62o) is modeled as a full correlation space. The DMRG prediction nearly overlaps with the energy curve from the coupled cluster with singles, doubles, and perturbative triple [CCSD(T)] calculations, while the multireference complete active space self-consistent field (CASSCF) calculations with the small reference configuration (8e,8o) are found to overestimate the biradical character of the electronic state of [Cu(2)O(2)](2+) according to the one-electron density matrix analysis.