Matrix Product State Wave Functions Research Articles

Excited-State DMRG Made Simple with FEAST

We introduce DMRG[FEAST], a new method for optimizing excited-state many-body wave functions with the density matrix renormalization group (DMRG) algorithm. Our approach applies the FEAST algorithm, originally designed for large-scale diagonalization problems, to matrix product state wave functions. We show that DMRG[FEAST] enables the stable optimization of both low- and high-energy eigenstates, therefore overcoming the limitations of state-of-the-art excited-state DMRG algorithms. We demonstrate the reliability of DMRG[FEAST] by calculating anharmonic vibrational excitation energies of molecules with up to 30 fully coupled degrees of freedom.

Simplified State Interaction for Matrix Product State Wave Functions.

We present an approximation to the state-interaction approach for matrix product state (MPS) wave functions (MPSSI) in a nonorthogonal molecular orbital basis, first presented by Knecht et al. [J. Chem. Theory Comput.,2016, 28, 5881], that allows for a significant reduction of the computational cost without significantly compromising its accuracy. The approximation is well-suited if the molecular orbital basis is close to orthogonality, and its reliability may be estimated a priori with a single numerical parameter. For an example of a platinum azide complex, our approximation offers up to 63-fold reduction in computational time compared to the original method for wave function overlaps and spin–orbit couplings, while still maintaining numerical accuracy.

Large classes of quantum scarred Hamiltonians from matrix product states

Motivated by the existence of exact many-body quantum scars in the AKLT chain, we explore the connection between Matrix Product State (MPS) wavefunctions and many-body quantum scarred Hamiltonians. We provide a method to systematically search for and construct parent Hamiltonians with towers of exact eigenstates composed of quasiparticles on top of an MPS wavefunction. These exact eigenstates have low entanglement in spite of being in the middle of the spectrum, thus violating the strong Eigenstate Thermalization Hypothesis (ETH). Using our approach, we recover the AKLT chain starting from the MPS of its ground state, and we derive the most general nearest-neighbor Hamiltonian that shares the AKLT quasiparticle tower of exact eigenstates. We further apply this formalism to other simple MPS wavefunctions, and derive new families of Hamiltonians that exhibit AKLT-like quantum scars. As a consequence, we also construct a scar-preserving deformation that connects the AKLT chain to the integrable spin-1 pure biquadratic model. Finally, we also derive other families of Hamiltonians that exhibit new types of exact quantum scars, including a $U(1)$-invariant perturbed Potts model.

Toward the efficient local tailored coupled cluster approximation and the peculiar case of oxo-Mn(Salen).

We introduce a new implementation of the coupled cluster method with single and double excitations tailored by the matrix product state wave functions (DMRG-TCCSD), which employs the local pair natural orbital (LPNO) approach. By exploiting locality in the coupled cluster stage of the calculation, we were able to remove some of the limitations that hindered the application of the canonical version of the method to larger systems and/or with larger basis sets. We assessed the accuracy of the approximation using two systems: tetramethyleneethane (TME) and oxo-Mn(Salen). Using the default cut-off parameters, we were able to recover over 99.7% and 99.8% of the canonical correlation energy for the triplet and singlet state of TME, respectively. In the case of oxo-Mn(Salen), we found that the amount of retrieved canonical correlation energy depends on the size of the complete active space (CAS)-we retrieved over 99.6% for the larger 27 orbital CAS and over 99.8% for the smaller 22 orbital CAS. The use of LPNO-TCCSD allowed us to perform these calculations up to quadruple-ζ basis set, amounting to 1178 basis functions. Moreover, we examined dependence of the ground state of oxo-Mn(Salen) on the CAS composition. We found that the inclusion of 4dxy orbital plays an important role in stabilizing the singlet state at the DMRG-CASSCF level via double-shell effect. However, by including dynamic correlation, the ground state was found to be triplet regardless of the size of the basis set or the composition of CAS, which is in agreement with previous findings by canonical DMRG-TCCSD in smaller basis.

Decoding quantum criticality from fermionic/parafermionic topological states

Under an appropriate symmetric bulk bipartition in a one-dimensional symmetry protected topological phase with the Affleck-Kennedy-Lieb-Tasaki matrix product state wave function for the odd integer spin chains, a bulk critical entanglement spectrum can be obtained, describing the excitation spectrum of the critical point separating the topological phase from the trivial phase with the same symmetry. Such a critical point is beyond the standard Landau-Ginzburg-Wilson paradigm for symmetry breaking phase transitions. Recently, the framework of matrix product states for topological phases with Majorana fermions/parafermions has been established. Here we first generalize these fixed-point matrix product states with the zero correlation length to the more generic ground-state wave functions with a finite correlation length for the general one-dimensional interacting Majorana fermion/parafermion systems. Then we employ the previous method to decode quantum criticality from the interacting Majorana fermion/parafermion matrix product states. The obtained quantum critical spectra are described by the conformal field theories with central charge $c\leq 1$, characterizing the quantum critical theories separating the fermionic/parafermionic topological phases from the trivial phases with the same symmetry.

Efficient Relativistic Density-Matrix Renormalization Group Implementation in a Matrix-Product Formulation.

We present an implementation of the relativistic quantum-chemical density matrix renormalization group (DMRG) approach based on a matrix-product formalism. Our approach allows us to optimize matrix product state (MPS) wave functions including a variational description of scalar-relativistic effects and spin-orbit coupling from which we can calculate, for example, first-order electric and magnetic properties in a relativistic framework. While complementing our pilot implementation ( Knecht , S. J. Chem. Phys. 2014 , 140 , 041101 ), this work exploits all features provided by its underlying nonrelativistic DMRG implementation based on an matrix product state and operator formalism. We illustrate the capabilities of our relativistic DMRG approach by studying the ground-state magnetization, as well as current density of a paramagnetic f9 dysprosium complex as a function of the active orbital space employed in the MPS wave function optimization.

Second-Order Self-Consistent-Field Density-Matrix Renormalization Group.

We present a matrix-product state (MPS)-based quadratically convergent density-matrix renormalization group self-consistent-field (DMRG-SCF) approach. Following a proposal by Werner and Knowles (J. Chem. Phys. 1985, 82, 5053), our DMRG-SCF algorithm is based on a direct minimization of an energy expression which is correct to second order with respect to changes in the molecular orbital basis. We exploit a simultaneous optimization of the MPS wave function and molecular orbitals in order to achieve quadratic convergence. In contrast to previously reported (augmented Hessian) Newton-Raphson and superconfiguration-interaction algorithms for DMRG-SCF, energy convergence beyond a quadratic scaling is possible in our ansatz. Discarding the set of redundant active-active orbital rotations, the DMRG-SCF energy converges typically within two to four cycles of the self-consistent procedure.

Correction to Coupled Cluster Method with Single and Double Excitations Tailored by Matrix Product State Wave Functions.

Correction to Coupled Cluster Method with Single and Double Excitations Tailored by Matrix Product State Wave Functions.

A Nonorthogonal State-Interaction Approach for Matrix Product State Wave Functions.

We present a state-interaction approach for matrix product state (MPS) wave functions in a nonorthogonal molecular orbital basis. Our approach allows us to calculate, for example, transition and spin-orbit coupling matrix elements between arbitrary electronic states, provided that they share the same one-electron basis functions and size of the active orbital space, respectively. The key element is the transformation of the MPS wave functions of different states from a nonorthogonal to a biorthonormal molecular orbital basis representation, by exploiting a sequence of nonunitary transformations, following a proposal by Malmqvist [Int. J. Quantum Chem. 1986, 30, 479]. This is well-known for traditional wave function parametrizations but has not yet been exploited for MPS wave functions.

Coupled Cluster Method with Single and Double Excitations Tailored by Matrix Product State Wave Functions.

In the past decade, the quantum chemical version of the density matrix renormalization group (DMRG) method has established itself as the method of choice for calculations of strongly correlated molecular systems. Despite its favorable scaling, it is in practice not suitable for computations of dynamic correlation. We present a novel method for accurate "post-DMRG" treatment of dynamic correlation based on the tailored coupled cluster (CC) theory in which the DMRG method is responsible for the proper description of nondynamic correlation, whereas dynamic correlation is incorporated through the framework of the CC theory. We illustrate the potential of this method on prominent multireference systems, in particular, N2 and Cr2 molecules and also oxo-Mn(Salen), for which we have performed the first post-DMRG computations in order to shed light on the energy ordering of the lowest spin states.

Tree Tensor Network State with Variable Tensor Order: An Efficient Multireference Method for Strongly Correlated Systems.

We study the tree-tensor-network-state (TTNS) method with variable tensor orders for quantum chemistry. TTNS is a variational method to efficiently approximate complete active space (CAS) configuration interaction (CI) wave functions in a tensor product form. TTNS can be considered as a higher order generalization of the matrix product state (MPS) method. The MPS wave function is formulated as products of matrices in a multiparticle basis spanning a truncated Hilbert space of the original CAS-CI problem. These matrices belong to active orbitals organized in a one-dimensional array, while tensors in TTNS are defined upon a tree-like arrangement of the same orbitals. The tree-structure is advantageous since the distance between two arbitrary orbitals in the tree scales only logarithmically with the number of orbitals N, whereas the scaling is linear in the MPS array. It is found to be beneficial from the computational costs point of view to keep strongly correlated orbitals in close vicinity in both arrangements; therefore, the TTNS ansatz is better suited for multireference problems with numerous highly correlated orbitals. To exploit the advantages of TTNS a novel algorithm is designed to optimize the tree tensor network topology based on quantum information theory and entanglement. The superior performance of the TTNS method is illustrated on the ionic-neutral avoided crossing of LiF. It is also shown that the avoided crossing of LiF can be localized using only ground state properties, namely one-orbital entanglement.

Matrix Product State, Quantum Entanglement, and Criticality in the One-Dimensional Dimerized Antiferromagnetic Heisenberg Model

The matrix product state (MPS) is utilized to investigate the ground state properties and quantum phase transitions (QPTs) of the dimerized antiferromagnetic Heisenberg (DAH) model. The ground state MPS wavefunctions determined by the infinite time-evolving block decimation (iTEBD) algorithm are shown to be very efficient descriptions of DAH model. In the thermodynamic limit, the quantum entanglement, the bond energy, and the nearest-neighbor correlations are calculated. It is revealed that the singular behavior of the bipartite entanglement can detect the QPTs directly. The critical point Jc2 = 1.0 is determined evidently, and the quantum phase transition is argued to belong to the second-order category. At the critical point, logarithmic divergent character of the block entanglement is observed, and the system can be described by a free bosonic field theory.

Matrix product state and quantum phase transitions in the one-dimensional extended quantum compass model

The matrix product state (MPS) is utilized to study the ground state properties and quantum phase transitions (QPTs) of the one-dimensional quantum compass model (QCM). The MPS wavefunctions are argued to be very efficient descriptions of QCM ground states, and are numerically determined by imaginary time projections. The ground state energy, correlations, quantum entanglement and its spectrum, local and nonlocal order parameters, etc., are calculated and studied in details. It is revealed that the bipartite and block entanglement entropies, as well as the nearest neighbor correlation functions can be used to detect the second-order QPTs, but not the first-order ones, while fidelity detections can recognize both. The entanglement spectrum is extracted from the MPS wavefunction, and found to be doubly degenerate in disordered phases of QCM, where non-local string order parameters exist. Moreover, with linearized tensor renormalization group method, the specific heat curves are evaluated and their low temperature behaviors are investigated.