Density Matrix Functional Theory Research Articles

Exploiting the Hessian for a Better Convergence of the SCF-RDMFT Procedure.

One-body reduced density matrix functional theory provides an alternative to density functional theory, which is able to treat static correlation while keeping a relatively low computation scaling. Its disadvantageous cost comes mainly from a slow convergence of the self-consistent energy optimization. To improve on that problem, we propose in this work the use of the Hessian of the energy, including the coupling term. We show that using the exact Hessian is very effective at reducing the number of iterations. However, since the exact Hessian is too expensive to use in practice, we propose an approximation based on an inexpensive exact part and BFGS updates.

Extracting many-body quantum resources within one-body reduced density matrix functional theory

Extracting many-body quantum resources within one-body reduced density matrix functional theory

Forcing broken symmetry to recover static electronic correlation: the H2 molecule test case

ABSTRACT A self-consistent field method based on a density matrix functional theory scheme is presented to compute the potential energy curve of the hydrogen molecule. A functional to recover the so-called cumulant correlation energy is introduced. The form of such functional is very simple being dependent explicitly only on the square of the overlap matrix element between the unrestricted non-orthogonal occupied orbitals of the calculation. The functional is a sum of two contributions referring to non-dynamic and dynamic correlation. The agreement with the full-CI potential energy curve is within chemical accuracy.

The convexity condition of density-functional theory.

It has long been postulated that within density-functional theory (DFT), the total energy of a finite electronic system is convex with respect to electron count so that 2Ev[N0] ≤ Ev[N0 - 1] + Ev[N0 + 1]. Using the infinite-separation-limit technique, this Communication proves the convexity condition for any formulation of DFT that is (1) exact for all v-representable densities, (2) size-consistent, and (3) translationally invariant. An analogous result is also proven for one-body reduced density matrix functional theory. While there are known DFT formulations in which the ground state is not always accessible, indicating that convexity does not hold in such cases, this proof, nonetheless, confirms a stringent constraint on the exact exchange-correlation functional. We also provide sufficient conditions for convexity in approximate DFT, which could aid in the development of density-functional approximations. This result lifts a standing assumption in the proof of the piecewise linearity condition with respect to electron count, which has proven central to understanding the Kohn-Sham bandgap and the exchange-correlation derivative discontinuity of DFT.

Short-range screened density matrix functional for proper descriptions of thermochemistry, thermochemical kinetics, nonbonded interactions, and singlet diradicals.

Common one-electron reduced density matrix (1-RDM) functionals that depend on Coulomb and exchange-only integrals tend to underestimate dynamic correlation, preventing reduced density matrix functional theory (RDMFT) from achieving comparable accuracy to density functional theory in main-group thermochemistry and thermochemical kinetics. The recently developed ωP22 functional introduces a semi-local density functional to screen the erroneous short-range portion of 1-RDM functionals without double-counting correlation, potentially providing a better treatment of dynamic correlation around equilibrium geometries. Herein, we systematically evaluate the performance of this functional model, which consists of two parameters, on main-group thermochemistry, thermochemical kinetics, nonbonded interactions, and more. Tests on atomization energies, vibrational frequencies, and reaction barriers reveal that the ωP22 functional model can reliably predict properties at equilibrium and slightly away from equilibrium geometries. In particular, it outperforms commonly used density functionals in the prediction of reaction barriers, nonbonded interactions, and singlet diradicals, thus enhancing the predictive power of RDMFT for routine calculations of thermochemistry and thermochemical kinetics around equilibrium geometries. Further development is needed in the future to refine short- and long-range approximations in the functional model in order to achieve an excellent description of properties both near and far from equilibrium geometries.

Self-consistent field method for open-shell systems within the density-matrix functional theory.

The unrestricted Hartree-Fock method is extended to correlation calculation within the density-matrix functional theory. The method is derived from an entropic cumulant functional for the correlation energy. The eigenvalue equations for the spin-orbitals are modified by the orbital occupation numbers. The Euler equation for the occupation numbers results in the Fermi-Dirac distribution, which is very efficient to update as soon as the orbital eigenvalue equations are solved. The method is demonstrated on the ground state of O .

Extending Conceptual Density Functional Theory toward First-Order Reduced Density Matrices: An Open Subsystems Viewpoint on the Fukui Matrix.

As a matrix extension of the Fukui function, a reactivity descriptor grounded within Conceptual Density Functional Theory, the Fukui matrix extends Frontier Molecular Orbital Theory to correlated regimes with its eigendecomposition in Fukui occupations and Fukui naturals. Despite successful applications, the questions remain as to whether replacing a quantity derived from a purely density-based framework by its matrix extension is theoretically well-founded and what chemical information is contained in the corresponding eigendecomposition. In this study, we show that the matrix extension of the Fukui function is only well-defined if one also generalizes the external potential to become nonlocal, leading to the introduction of Conceptual First-Order Reduced Density Matrix Functional Theory. By interpreting the Anderson impurity model from an interacting open subsystem perspective, we show how Fukui occupations and Fukui naturals reflect the influence of an increasing (static) correlation and which characteristic patterns we should expect within a molecular context. This study represents a step in generalizing Conceptual Density Functional Theory beyond its density-based perspective.

A unified density matrix functional construction of quantum baths in density matrix embedding theory beyond the mean-field approximation.

The equivalence in one-electron quantum baths between the practical implementation of density matrix embedding theory (DMET) and the more recent Householder-transformed density matrix functional embedding theory has been shown previously in the standard but special case where the reference full-size (one-electron reduced) density matrix, from which the bath is constructed, is idempotent [S. Yalouz et al., J. Chem. Phys. 157, 214112 (2022)]. We prove mathematically that the equivalence remains valid when the density matrix is not idempotent anymore, thus allowing for the construction of correlated (one-electron) quantum baths. A density-matrix functional exactification of DMET is derived within the present unified quantum embedding formalism. Numerical examples reveal that the embedding cluster can be quite sensitive to the level of density-matrix functional approximation used for computing the reference density matrix.

Refining and relating fundamentals of functional theory.

To advance the foundation of one-particle reduced density matrix functional theory (1RDMFT), we refine and relate some of its fundamental features and underlying concepts. We define by concise means the scope of a 1RDMFT, identify its possible natural variables, and explain how symmetries could be exploited. In particular, for systems with time-reversal symmetry, we explain why there exist six equivalent universal functionals, prove concise relations among them, and conclude that the important notion of v-representability is relative to the scope and choice of variable. All these fundamental concepts are then comprehensively discussed and illustrated for the Hubbard dimer and its generalization to arbitrary pair interactions W. For this, we derive by analytical means the pure and ensemble functionals with respect to both the real- and complex-valued Hilbert space. The comparison of various functionals allows us to solve the underlying v-representability problems analytically, and the dependence of its solution on the pair interaction is demonstrated. Intriguingly, the gradient of each universal functional is found to always diverge repulsively on the boundary of the domain. In that sense, this key finding emphasizes the universal character of the fermionic exchange force, recently discovered and proven in the context of translationally invariant one-band lattice models.

Deriving density-matrix functionals for excited states

We initiate the recently proposed ww-ensemble one-particle reduced density matrix functional theory (ww-RDMFT) by deriving the first functional approximations and illustrate how excitation energies can be calculated in practice. For this endeavour, we first study the symmetric Hubbard dimer, constituting the building block of the Hubbard model, for which we execute the Levy-Lieb constrained search. Second, due to the particular suitability of ww-RDMFT for describing Bose-Einstein condensates, we demonstrate three conceptually different approaches for deriving the universal functional in a homogeneous Bose gas for arbitrary pair interaction in the Bogoliubov regime. Remarkably, in both systems the gradient of the functional is found to diverge repulsively at the boundary of the functional’s domain, extending the recently discovered Bose-Einstein condensation force to excited states. Our findings highlight the physical relevance of the generalized exclusion principle for fermionic and bosonic mixed states and the curse of universality in functional theories.

Effective local potentials for density and density-matrix functional approximations with non-negative screening density.

A way to improve the accuracy of the spectral properties in density functional theory (DFT) is to impose constraints on the effective, Kohn-Sham (KS), local potential [J. Chem. Phys. 136, 224109 (2012)]. As illustrated, a convenient variational quantity in that approach is the "screening" or "electron repulsion" density, ρrep, corresponding to the local, KS Hartree, exchange and correlation potential through Poisson's equation. Two constraints, applied to this minimization, largely remove self-interaction errors from the effective potential: (i) ρrep integrates to N - 1, where N is the number of electrons, and (ii) ρrep ≥ 0 everywhere. In this work, we introduce an effective "screening" amplitude, f, as the variational quantity, with the screening density being ρrep = f2. In this way, the positivity condition for ρrep is automatically satisfied, and the minimization problem becomes more efficient and robust. We apply this technique to molecular calculations, employing several approximations in DFT and in reduced density matrix functional theory. We find that the proposed development is an accurate, yet robust, variant of the constrained effective potential method.

Calculation of the ELF in the excited state with single-determinant methods.

Since its first definition, back in 1990, the electron localization function (ELF) has settled as one of the most commonly employed techniques to characterize the nature of the chemical bond in real space. Although most of the work using the ELF has focused on the study of ground-state chemical reactivity, a growing interest has blossomed to apply these techniques to the nearly unexplored realm of excited states and photochemistry. Since accurate excited electronic states usually require to account appropriately for electron correlation, the standard single-determinant ELF formulation cannot be blindly applied to them, and it is necessary to turn to correlated ELF descriptions based on the two-particle density matrix (2-PDM). The latter requires costly wavefunction approaches, unaffordable for most of the systems of current photochemical interest. Here, we compare the exact, 2-PDM-based ELF results with those of approximate 2-PDM reconstructions taken from reduced density matrix functional theory. Our approach is put to the test in a wide variety of representative scenarios, such as those provided by the lowest-lying excited electronic states of simple diatomic and polyatomic molecules. Altogether, our results suggest that even approximate 2-PDMs are able to accurately reproduce, on a general basis, the topological and statistical features of the ELF scalar field, paving the way toward the application of cost-effective methodologies, such as time-dependent-Hartree-Fock or time-dependent density functional theory, in the accurate description of the chemical bonding in excited states of photochemical relevance.

One-body reduced density-matrix functional theory for the canonical ensemble

We establish one-body reduced density-matrix functional theory for the canonical ensemble in a finite basis set at an elevated temperature. Including temperature guarantees differentiability of the universal functional by occupying all states and additionally not fully occupying the states in a fermionic system. We use convexity of the universal functional and invertibility of the potential-to-1RDM map to show that the subgradient contains only one element which is equivalent to differentiability. This allows us to show that all 1RDMs with a purely fractional occupation number spectrum ($0 < n_i < 1 \; \forall_i$) are uniquely $v$-representable up to a constant.

Density-matrix functional theory of the attractive Hubbard model: Statistical analogy of pairing correlations

The ground-state properties of the Hubbard model with attractive local pairing interactions are investigated in the framework of lattice density-functional theory. A remarkable correlation is revealed between the interaction-energy functional $W[\mathbit{\ensuremath{\eta}}]$ corresponding to the Bloch-state occupation-number distribution ${\ensuremath{\eta}}_{\ensuremath{\kappa}\ensuremath{\sigma}}$ and the entropy $S[\mathbit{\ensuremath{\eta}}]$ of a system of noninteracting fermions having the same ${\ensuremath{\eta}}_{\mathbit{k}\ensuremath{\sigma}}$. The relation between $W[\mathbit{\ensuremath{\eta}}]$ and $S[\mathbit{\ensuremath{\eta}}]$ is shown to be approximately linear for a wide range of ground-state representable occupation-number distributions ${\ensuremath{\eta}}_{\mathbit{k}\ensuremath{\sigma}}$. Taking advantage of this statistical analogy, a simple explicit ansatz for $W[\mathbit{\ensuremath{\eta}}]$ of the attractive Hubbard model is proposed, which can be applied to arbitrary periodic systems. The accuracy of this approximation is demonstrated by calculating the main ground-state properties of the model on several 1D and 2D bipartite and nonbipartite lattices and by comparing the results with exact diagonalizations.

Comparison of Density-Matrix Corrections to Density Functional Theory.

Density functional theory (DFT), one of the most widely utilized methods available to computational chemistry, fails to describe systems with statically correlated electrons. To address this shortcoming, in previous work, we transformed DFT into a one-electron reduced density matrix theory (1-RDMFT) via the inclusion of a quadratic one-electron reduced density matrix (1-RDM) correction. Here, we combine our 1-RDMFT approach with different DFT functionals as well as Hartree-Fock to elucidate the method's dependence on the underlying functional selection. Furthermore, we generalize the information density matrix functional theory (iDMFT), recently developed as a correction to the Hartree-Fock method, by incorporating density functionals in place of the Hartree-Fock functional. We relate iDMFT mathematically to our approach and benchmark the two with a common set of functionals and systems.

Reduced density matrix functional theory from an ab initio seniority-zero wave function: Exact and approximate formulations along adiabatic connection paths

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.

Parallel quantum chemistry on noisy intermediate-scale quantum computers

A novel parallel hybrid quantum-classical algorithm for the solution of the quantum-chemical ground-state energy problem on gate-based quantum computers is presented. This approach is based on the reduced density-matrix functional theory (RDMFT) formulation of the electronic structure problem. For that purpose, the density-matrix functional of the full system is decomposed into an indirectly coupled sum of density-matrix functionals for all its subsystems using the adaptive cluster approximation to RDMFT. The approximations involved in the decomposition and the adaptive cluster approximation itself can be systematically converged to the exact result. The solutions for the density-matrix functionals of the effective subsystems involves a constrained minimization over many-particle states that are approximated by parametrized trial states on the quantum computer similarly to the variational quantum eigensolver. The independence of the density-matrix functionals of the effective subsystems introduces a new level of parallelization and allows for the computational treatment of much larger molecules on a quantum computer with a given qubit count. In addition, for the proposed algorithm techniques are presented to reduce the qubit count, the number of quantum programs, as well as its depth. The new approach is demonstrated for Hubbard-like systems on IBM quantum computers based on superconducting transmon qubits.

Explicit-by-Implicit Treatment of Natural Orbital Occupations Using First- and Second-Order Optimization Algorithms: A Comparative Study.

To address the convergence issues in the natural occupation optimization of reduced density matrix functional theory (RDMFT), we recently proposed the explicit-by-implicit (EBI) idea to handle the ensemble N-representability constraint (Yao et al. J. Phys. Chem. Lett. 2021, 12, 6788). This work continues to focus on these issues that can affect the reliability of the electronic structure description in RDMFT; further explores the combination of EBI, as well as the (augmented) Lagrangian methods (both LM and ALM), with both first- and second-order numerical optimization algorithms; and carefully evaluates their performances in natural occupation optimizations of various systems, including strongly correlated systems and large molecules. By comparing both converged energies and elapsed times, it can be seen that the LM and ALM have serious convergence issues for systems of different sizes. In contrast, the optimizations of EBI can converge to better energies with fewer iterations. However, due to the local convergence nature of the Newton's Method (NM) algorithm, EBI@NM still suffers from the local minimum issue for both strongly correlated systems and large molecules. Overall, the combination of EBI with the simple first-order algorithm of gradient descent (GD), namely EBI@GD, consistently provides the lowest converged energies for different types of systems, with the lowest computational scaling. These tests demonstrate the advantages of EBI in the calculations of transition states, strongly correlated systems, and large molecules. Meanwhile, the insights gained from this work are helpful to further develop more efficient algorithms for RDMFT.

Introducing screening in one-body density matrix functionals: Impact on charged excitations of model systems via the extended Koopmans' theorem

In this work we get insight into the impact of reduced density matrix functionals on the quality of removal/addition energies obtained using the extended Koopmans' theorem (EKT). Within the reduced density matrix functional theory (RDMFT) the EKT approach reduces to a matrix diagonalization, whose ingredients are the one- and two-body reduced density matrices. A striking feature of the EKT within RDMFT is that it opens a band gap, although it is too large, in strongly correlated materials, which are a challenge for state-of-the-art methods such as $GW$. Using the one-dimensional Hubbard model and the homogeneous electron gas as test cases, we find that (i) with exact or very accurate density matrices the EKT systematically overestimates the band gap in the Hubbard model and the bandwidth in the homogeneous electron gas and (ii) with approximate density matrices, instead, the EKT can benefit from error cancellation. In particular we test a new approximation which combines random-phase approximation screening with the power functional approximation to the two-body reduced density matrix introduced by Sharma et al. [Phys. Rev. B 78, 201103 (2008)]. An important feature of this approximation is that it reduces the EKT band gap in the studied models; it is hence a promising approximation for correcting the EKT band-gap overestimation in strongly correlated materials.

Relativistic reduced density matrix functional theory.

As a new approach to efficiently describe correlation effects in the relativistic quantum world we propose to consider reduced density matrix functional theory, where the key quantity is the first-order reduced density matrix (1-RDM). In this work, we first introduce the theoretical foundations to extend the applicability of this theory to the relativistic domain. Then, using the so-called no-pair (np) approximation, we arrive at an approximate treatment of the relativistic effects by focusing on electronic wavefunctions and neglecting explicit contributions from positrons. Within the np approximation the theory becomes similar to the nonrelativistic case, with as unknown only the functional that describes the electron-electron interactions in terms of the 1-RDM. This requires the construction of functional approximations, and we therefore also present the relativistic versions of some common RDMFT approximations that are used in the nonrelativistic context and discuss their properties.