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Context: In the realm of quantum chemistry, the accurate prediction of electronic structure and properties of nanostructures remains a formidable challenge. Density functional theory (DFT) and density matrix renormalization group (DMRG) have emerged as two powerful computational methods for addressing electronic correlation effects in diverse molecular systems. We compare ground-state energies ( e 0 ), density profiles ( n ), and average entanglement entropies ( S ¯ ) in metals, insulators and at the transition from metal to insulator, in homogeneous, superlattices, and harmonically confined chains described by the fermionic one-dimensional Hubbard model. While for the homogeneous systems, there is a clear hierarchy between the deviations, D % (S ¯) < D % (e 0) < D ¯ % (n) , and all the deviations decrease with the chain size; for superlattices and harmonic confinement, the relation among the deviations is less trivial and strongly dependent on the superlattice structure and the confinement strength considered. For the superlattices, in general, increasing the number of impurities in the unit cell represents lower precision in the DFT calculations. For the confined chains, DFT performs better for metallic phases, while the highest deviations appear for the Mott and band-insulator phases. This work provides a comprehensive comparative analysis of these methodologies, shedding light on their respective strengths, limitations, and applications. Methods: The DFT calculations were performed using the standard Kohn-Sham scheme within the BALDA approach. It integrated the numerical Bethe-Ansatz (BA) solution of the Hubbard model as the homogeneous density functional within a local-density approximation (LDA) for the exchange-correlation energy. The DMRG algorithms were implemented using the ITensor library, which is based on the matrix product states (MPS) ansatz. The calculations were performed until the energy reaches convergence of at least 10 - 8 . [ABSTRACT FROM AUTHOR]

In this paper, we investigate the convergence properties of density matrix renormalisation group (DMRG) calculations for vertical electronic excitations performed on three bimolecular complexes motivated by Szalay's recent benchmark results [JCTC. 2020;16:7]. Besides the high-level coupled-cluster reference spectrum, the extrapolated truncation-free DMRG results are compared against several alternative solutions based on multireference configuration interaction and coupled-cluster theories. By taking advantage of the error cancellation effects, which are inherent in the state-averaged computational scheme, we demonstrate that the extrapolated solution based on only low bond-dimensional DMRG data could already provide quantitative predictions even for large active spaces. We also show that orbital optimisation improves further the accuracy of the DMRG results which systematically approach the excitation energies of coupled cluster single-double-triple at similar computational costs. [ABSTRACT FROM AUTHOR]

One of the most powerful and popular quantum entanglement-based computation methods for the simulation of one-dimensional and quasi-two-dimensional strongly correlated materials is the Density Matrix Renormalization Group (DMRG) technique. A lower quantum entanglement between the system’s degrees of freedom will result in a higher accuracy of the method. However, quantum entanglement between two complementary subsystems of a closed system depends on how the degrees of freedom have been distributed between them, and therefore, it is not in general invariant under arbitrary unitary transformations. Entanglement is invariant only under those unitary transformations which do not mix the degrees of freedom associated with the two subsystems. Consequently, a fundamental question is that if it is possible to construct, algorithmically, unitary transformations which minimize entanglement between degrees of freedom of the system and therefore maximize the DMRG technique? A general solution to this problem is highly nontrivial in general. In this paper, we study interacting fermionic models and by considering single-particle unitary transformations only. We define a novel and efficient method to find the optimal single-particle unitary transformations. In this framework, we show that using our algorithm, the accuracy of the DMRG method at a given bond dimension is increased and the ground-state energy is decreased and approaches to its exact value. Our method paves the way toward finding more general (many-particle) optimized unitary transformations and helps us to better understand the behavior of fermions in strongly correlated materials.

In this paper, the spin ladder consisting of two antiferromagnetic Heisenberg legs is investigated by means of the density matrix renormalization group method with its matrix product state form. The energy density and bipartite entanglement measured by concurrence are calculated, the effects of interleg couplings and open boundary condition on entanglement distributions are discussed in detail when the interleg couplings are ferro- and antiferromagnetic, respectively. We found that the entanglements are mainly distributed in legs and diagonals when the interleg couplings are ferromagnetic and in rungs when the couplings are antiferromagnetic. Furthermore, the intraleg entanglements are more affected by the dimerization caused by open boundary than interleg ones. Specifically, that dimerization will be weakened by the interleg couplings, and the entanglements are distributed more uniformly. [ABSTRACT FROM AUTHOR]

The simulations of spectroscopy and quantum dynamics are of vital importance to the understanding of the electronic processes in complex systems, including the radiative/radiationless electronic relaxation relevant for optical emission, charge/energy transfer in molecular aggregates related to carrier mobility in organic materials, as well as photovoltaic and thermoelectric conversion, light‐harvesting and spin transport, and so forth. In recent years, time‐dependent density matrix renormalization group (TD‐DMRG) has emerged as a general, numerically accurate and efficient method for high‐dimensional full‐quantum dynamics. This review will cover the fundamental algorithms of TD‐DMRG in the modern framework of matrix product states (MPS) and matrix product operators (MPO), including the basic algebra with respect to MPS and MPO, the novel time evolution schemes to propagate MPS, and the automated MPO construction algorithm to encode generic Hamiltonian. Most importantly, the proposed method can handle the mixed state density matrix at finite temperature, enabling quantum statistical description for molecular aggregates. We demonstrate the performance of TD‐DMRG by benchmarking with the current state‐of‐the‐art methods for simulating quantum dynamics of the spin‐boson model and the Frenkel–Holstein(–Peierls) model. As applications of TD‐DMRG to real‐world problems, we present theoretical investigations of carrier mobility and spectral function of rubrene crystal, and the radiationless decay rate of azulene with an anharmonic potential energy surface. This article is categorized under:Theoretical and Physical Chemistry > Statistical MechanicsTheoretical and Physical Chemistry > Reaction Dynamics and KineticsSoftware > Simulation Methods [ABSTRACT FROM AUTHOR]

Phenalenyl (C 13 H 9 ) is an open-shell spin-1/2 nanographene. Using scanning tunneling microscopy (STM) inelastic electron tunneling spectroscopy (IETS), covalently bonded phenalenyl dimers have been shown to feature conductance steps associated with singlet-triplet excitations of a spin-1/2 dimer with antiferromagnetic exchange. Here, we address the possibility of tuning the magnitude of the exchange interactions by varying the dihedral angle between the two molecules within a dimer. Theoretical methods ranging from density functional theory calculations to many-body model Hamiltonians solved within different levels of approximation are used to explain STM-IETS measurements of phenalenyl dimers on a hexagonal boron nitride (h-BN)/Rh(111) surface, which exhibit signatures of twisting. By means of first-principles calculations, we also propose strategies to induce sizable twist angles in surface-adsorbed phenalenyl dimers via functional groups, including a photoswitchable scheme. This work paves the way toward tuning magnetic couplings in carbon-based spin chains and two-dimensional lattices.

The cluster mean-field with density matrix renormalization (CMFT + DMRG) method which combines the simplicity of the mean-field theory and the numerical power of the density-matrix renormalization group method is applied to understand the quantum phases of the one-dimensional Boseâ€"Hubbard models. We show that the CMFT + DMRG method is an effective numerical technique with moderate computational resources to determine relevant order parameters and correlation functions of large one-dimensional systems. We apply the CMFT + DMRG for the Bose Hubbard and extended Bose Hubbard models to account for the superfluid, Mott insulator, and density wave phases in these models. Our results are in good agreement with the known phase diagram of these models, demonstrating the efficacy of this method. [ABSTRACT FROM AUTHOR]

In this work, the cross derivative of the Gibbs free energy, initially proposed for phase transitions in classical spin models (Chen et al 2020 Phys. Rev. B 101 165123), is extended for quantum systems. We take the spin-1 XXZ chain with anisotropies as an example to demonstrate its effectiveness and convenience for the Gaussian-type quantum phase transitions therein. These higher-order transitions are very challenging to determine by conventional methods. From the cross derivative with respect to the two anisotropic strengths, a single valley structure is observed clearly in each system size. The finite-size extrapolation of the valley depth shows a perfect logarithmic divergence, signaling the onset of a phase transition. Meanwhile, the critical point and the critical exponent for the correlation length are obtained by a power-law fitting of the valley location in each size. The results are well consistent with the best estimations in the literature. Its application to other quantum systems with continuous phase transitions is also discussed briefly.

In this paper, the quantum entanglement (concurrence) of one-dimensional antiferromagnetic XXZ spin system with alternating nearest-neighbor interactions is studied by means of the density matrix renormalization group method with matrix product state form. The ground-state energy, long-distance entanglement and entanglement distribution are calculated, and the effects of alternating interactions, anisotropy and open boundary condition on them are discussed. It is found that the alternating interactions favor the generation and development of long-distance entanglement, while anisotropy inhibits that. For the entanglement distribution of the system, it is also found that the alternating interactions and open boundary condition induce the dimerization on odd and even bonds, respectively, while anisotropy always suppresses this behavior. Furthermore, both nearest-neighbor and long-distance entanglements are converged to certain values with increasing system size. • Long-distance entanglement is strengthened by alternating interactions. • OBC and alternating couplings make the dimerization on odd and even bonds, respectively. • Anisotropy always inhibits dimerization caused by OBC or alternating interactions. [ABSTRACT FROM AUTHOR]

Density matrix renormalization group (DMRG) and its time-dependent variants have found widespread applications in quantum chemistry, including ab initio electronic structure of complex bio-molecules, spectroscopy for molecular aggregates, and charge transport in bulk organic semiconductors. The underlying wavefunction ansatz for DMRG, matrix product state (MPS), requires mapping degrees of freedom (DOF) into a one-dimensional topology. DOF ordering becomes a crucial factor for DMRG accuracy. In this work, we propose swapping neighboring DOFs during the DMRG sweeps for DOF ordering, which we term 'on the fly swapping' (OFS) algorithm. We show that OFS is universal for both static and time-dependent DMRG with minimum computational overhead. Examples are given for one dimensional antiferromagnetic Heisenberg model, ab initio electronic structure of N 2 molecule, and the S 1 /S 2 internal conversion dynamics of pyrazine molecule. It is found that OFS can indeed improve accuracy by finding better DOF ordering in all cases., (© 2022 IOP Publishing Ltd.)