Electronic Hamiltonian Research Articles

Non-adiabatic quantum dynamics without potential energy surfaces based on second-quantized electrons: Application within the framework of the MCTDH method.

A first principles quantum formalism to describe the non-adiabatic dynamics of electrons and nuclei based on a second quantization representation (SQR) of the electronic motion combined with the usual representation of the nuclear coordinates is introduced. This procedure circumvents the introduction of potential energy surfaces and non-adiabatic couplings, providing an alternative to the Born-Oppenheimer approximation. An important feature of the molecular Hamiltonian in the mixed first quantized representation for the nuclei and the SQR representation for the electrons is that all degrees of freedom, nuclear positions and electronic occupations, are distinguishable. This makes the approach compatible with various tensor decomposition Ansätze for the propagation of the nuclear-electronic wavefunction. Here, we describe the application of this formalism within the multi-configuration time-dependent Hartree framework and its multilayer generalization, corresponding to Tucker and hierarchical Tucker tensor decompositions of the wavefunction, respectively. The approach is applied to the calculation of the photodissociation cross section of the HeH+ molecule under extreme ultraviolet irradiation, which features non-adiabatic effects and quantum interferences between the two possible fragmentation channels, He + H+ and He+ + H. These calculations are compared with the usual description based on ab initio potential energy surfaces and non-adiabatic coupling matrix elements, which fully agree. The proof-of-principle calculations serve to illustrate the advantages and drawbacks of this formalism, which are discussed in detail, as well as possible ways to overcome them. We close with an outlook of possible application domains where the formalism might outperform the usual approach, for example, in situations that combine a strong static correlation of the electrons with non-adiabatic electronic-nuclear effects.

Machine learning a molecular Hamiltonian for predicting electron dynamics

We develop a computational method to learn a molecular Hamiltonian matrix from matrix-valued time series of the electron density. As we demonstrate for three small molecules, the resulting Hamiltonians can be used for electron density evolution, producing highly accurate results even when propagating 1,000 time steps beyond the training data. As a more rigorous test, we use the learned Hamiltonians to simulate electron dynamics in the presence of an applied electric field, extrapolating to a problem that is beyond the field-free training data. We find that the resulting electron dynamics predicted by our learned Hamiltonian are in close quantitative agreement with the ground truth. Our method relies on combining a reduced-dimensional, linear statistical model of the Hamiltonian with a time-discretization of the quantum Liouville equation within time-dependent Hartree Fock theory. We train the model using a least-squares solver, avoiding numerous, CPU-intensive optimization steps. For both field-free and field-on problems, we quantify training and propagation errors, highlighting areas for future development.

An intervening metallic phase at the CDW–SDW transition region in the one-dimensional Holstein-Hubbard model at half filling: a semi-exact solution

The one-dimensional Holstein–Hubbard model is analyzed at half filling at the CDW-SDW transition region by using a series of unitary transformations. The phonon degrees of freedom are eliminated by averaging the transformed Hamiltonian with respect to a generalized many-phonon state and the resulting effective electronic Hamiltonian is finally solved exactly by employing the Bethe-ansatz technique. The present variational state leads to a lower ground state energy as compared to those obtained from the previous variational calculations and yields a wider intermediate metallic phase at the SDW-CDW transition region confirming the prediction of Takada and Chatterjee.

Disorder-induced quantum phase transitions in three-dimensional second-order topological insulators

Disorder effects on three-dimensional second-order topological insulators (3DSOTIs) are investigated numerically and analytically. The study is based on a tight-binding Hamiltonian for non-interacting electrons on a cubic lattice with a reflection symmetry that supports a 3DSOTI in the absence of disorder. Interestingly, unlike the disorder effects on a topological trivial system that can only be either a diffusive metal (DM) or an Anderson insulator (AI), disorders can sequentially induce four phases of 3DSOTIs, three-dimensional first-order topologicalinsulators (3DFOTIs), DMs and AIs. At a weak disorder when the on-site random potential of strength $W$ is below a low critical value $W_{c1}$ at which the gap of surface states closes while the bulk sates are still gapped, the system is a disordered 3DSOTI characterized by a constant density of states and a quantized integer conductance of $e^2/h$ through its chiral hinge states. The gap of the bulk states closes at a higher critical disorder $W_{c2}$, and the system is a disordered 3DFOTI in a lower intermediate disorder between $W_{c1}$ and $W_{c2}$ in which electron conduction is through the topological surface states. The system becomes a DM in a higher intermediate disorder between $W_{c2}$ and $W_{c3}$ above which the states at the Fermi level are localized. It undergoes a normal three-dimension metal-to-insulator transition at $W_{c3}$ and becomes the conventional AI for $W>W_{c3}$. The self-consistent Born approximation allows one to see how the density of bulk states and the Dirac mass are modified by the on-site disorders.

Decoherence-corrected Ehrenfest molecular dynamics on many electronic states.

Decoherence corrections increase the accuracy of mixed quantum-classical nonadiabatic molecular dynamics methods, but they typically require explicit knowledge of the potential energy surfaces of all occupied electronic states. This requirement renders them impractical for applications in which large numbers of electronic states are occupied. The authors recently introduced the collapse to a block (TAB) decoherence correction [M. P. Esch and B. G. Levine, J. Chem. Phys. 152, 234105 (2020)], which incorporates a state-pairwise definition of decoherence time to accurately describe dynamics on more than two electronic states. In this work, TAB is extended by introduction of a scheme for efficiently computing a small number of approximate eigenstates of the electronic Hamiltonian, eliminating the need for explicit knowledge of a large number of potential energy surfaces. This adaptation of TAB for dense manifolds of states (TAB-DMS) is systematically improvable by increasing the number of computed approximate eigenstates. Application to a series of one-dimensional model problems demonstrates that TAB-DMS can be accurate when even a very modest number of approximate eigenstates are computed (four in all models tested here). Comparison of TAB simulations to exact quantum dynamical simulations indicates that TAB is quite accurate so long as the decoherence correction is carefully parameterized.

Non-adiabatic coupling as a frictional force in (He, H, H)+ dynamics and the formation of HeH2 +

It is shown that the Born–Oppenheimer–Huang non-adiabatic coupling terms (NACTs) in a molecular Hamiltonian can be considered as equivalent to a friction force in classical mechanics and consequently responsible for the formation of triatomic species like HeH. The classical equation of motion is solved accordingly for a test case of a helium atom approaching an H molecule at its potential minimum along the collinear axis and lines parallel to it and also for the C geometry. It is shown that the singular NACTs between the first two excited states slow down the motion of the three quasi-ions (He, H, H) while approaching each other and result in substantial loss of kinetic energy in the collision process. These results have profound implications for the formation of di- and triatomic species in the early universe, during the chemical synthesis epoch following the nucleosynthesis that followed the Big Bang.

On general-relativistic hydrogen and hydrogenic ions

This paper studies how the static non-linear electromagnetic-vacuum spacetime of a point nucleus with a negative bare mass affects the self-adjointness of the general-relativistic Dirac Hamiltonian for a test electron, without and with an anomalous magnetic moment. This study interpolates between the previously studied extreme cases of a test electron in (a) the Reissner–Weyl–Nordström spacetime (Maxwell’s electromagnetic vacuum), which sports a very strong curvature singularity with negative infinite bare mass, and (b) the Hoffmann spacetime (Born or Born–Infeld’s electromagnetic vacuum) with vanishing bare mass, which features the mildest possible curvature singularity. The main conclusion reached is: on electrostatic spacetimes of a point nucleus with a strictly negative bare mass (which may be −∞), essential self-adjointness fails unless the radial electric field diverges sufficiently fast at the nucleus and the anomalous magnetic moment of the electron is taken into account. Thus, on the Hoffmann spacetime with a (strictly) negative bare mass, the Dirac Hamiltonian of a test electron, with or without anomalous magnetic moment, is not essentially self-adjoint. All these operators have self-adjoint extensions, though, with the usual essential spectrum (−∞, −mec2] ∪ [mec2, ∞) and an infinite discrete spectrum located in the gap (−mec2, mec2).

Coherent Control of Internal Conversion in Strong-Field Molecular Ionization.

We demonstrate coherent control over internal conversion during strong-field molecular ionization with shaped, few-cycle laser pulses. The control is driven by interference in different neutral states, which are coupled via non-Born-Oppenheimer terms in the molecular Hamiltonian. Our measurements highlight the preservation of electronic coherence in nonadiabatic transitions between electronic states.

Relativistic pseudo Renner effect of (3Π + 1Σ+) × π type in linear triatomic molecules

We present here two-electronic model, which describes singlet–triplet interaction of electronic terms 1Σ+ and 3Π in the linear triatomic molecules. Our analysis takes into account spin-orbital coupling terms in ab initio form of Breit-Pauli operator and uses symmetry properties of electronic Hamiltonian. It is shown that the symmetry operators of electronic Hamiltonian include both space operators and matrix operators.In our analysis we take into account only deformation π-modes. Resulting 7 × 7 vibronic matrix describes really relativistic pseudo Renner effect (3Π + 1Σ+) × π. Eigenvalues of vibronic matrix (i.e. potential energy surfaces) have axial symmetry.

Relativistic Renner Effect 4Π × π

The paper considers the relativistic Renner effect 4Π × π, which occurs in linear triatomic molecules containing heavy atoms. The vibronic matrix is calculated in the three-electron model. The electronic Hamiltonian is expanded in a Taylor series in π-modes taking into account the terms of the main, first, and second orders. To calculate nonzero elements in the vibronic matrix, group selection rules and vibronic symmetry operators are used to minimize the number of independent parameters in the vibronic matrix. The vibronic matrix has a dimension of 8 × 8 and its eigenvalues (potential surfaces) can be calculated only by numerical methods.

Measurement reduction in variational quantum algorithms

Variational quantum algorithms are promising applications of noisy intermediate-scale quantum (NISQ) computers. These algorithms consist of a number of separate prepare-and-measure experiments that estimate terms in a Hamiltonian. The number of terms can become overwhelmingly large for problems at the scale of NISQ hardware that may soon be available. We approach this problem from the perspective of contextuality, and use unitary partitioning (developed independently by Izmaylov et al. [J. Chem. Theory Comput. 16, 190 (2020)]) to define variational quantum eigensolver procedures in which additional unitary operations are appended to the ansatz preparation to reduce the number of terms. This approach may be scaled to use all coherent resources available after ansatz preparation. We also study the use of asymmetric qubitization to implement the additional coherent operations with lower circuit depth. We investigate this technique for lattice Hamiltonians, random Pauli Hamiltonians, and electronic structure Hamiltonians. Using this technique, we find a constant factor speedup for lattice and random Pauli Hamiltonians. For electronic structure Hamiltonians, we prove that linear term reduction with respect to the number of orbitals, which has been previously observed in numerical studies, is always achievable. For systems represented on 10--30 qubits, we find that there is a reduction in the number of terms by approximately an order of magnitude. Applied to the plane-wave dual basis representation of fermionic Hamiltonians, however, unitary partitioning offers only a constant factor reduction. Finally, we show that noncontextual Hamiltonians may be reduced to effective commuting Hamiltonians using unitary partitioning.

Polaritonic coupled-cluster theory

We develop coupled-cluster theory for systems of electrons strongly coupled to photons, providing a promising theoretical tool in polaritonic chemistry with a perspective of application to all types of fermion-boson coupled systems. We show benchmark results for model molecular Hamiltonians coupled to cavity photons. By comparing to full configuration interaction results for various ground-state properties and optical spectra, we demonstrate that our method captures all key features present in the exact reference, including Rabi splittings and multi-photon processes. Further, a path on how to incorporate our bosonic extension of coupled-cluster theory into existing quantum chemistry programs is given.

Molecular parity nonconservation in nuclear spin couplings

The weak interaction does not conserve parity, which is apparent in many nuclear and atomic phenomena. However, thus far, parity nonconservation has not been observed in molecules. Here we consider nuclear-spin-dependent parity nonconserving contributions to the molecular Hamiltonian. These contributions give rise to a parity nonconserving indirect nuclear spin-spin coupling which can be distinguished from parity conserving interactions in molecules of appropriate symmetry, including diatomic molecules. We estimate the magnitude of the coupling, taking into account relativistic corrections. Finally, we propose and simulate an experiment to detect the parity nonconserving coupling using liquid- or gas-state zero-field nuclear magnetic resonance of electrically oriented molecules and show that $^{1}$H$^{19}$F should give signals within the detection limits of current atomic vapor-cell magnetometers.

D -wave superconductivity and Bogoliubov-Fermi surfaces in Rarita-Schwinger-Weyl semimetals

We uncover the properties of complex tensor (d-wave) superconducting order in three-dimensional Rarita-Schwinger-Weyl semimetals that host pseudospin-3/2 fermions at a fourfold linear band crossing point. Although the general theory of d-wave order was originally developed for materials displaying quadratic band touching, it directly applies to the case of semimetals with linear dispersion, several candidate compounds of which have been discovered experimentally very recently. The spin-3/2 nature of the fermions allows for the formation of spin-2 Cooper pairs which may be described by a complex second-rank tensor order parameter. In the case of linear dispersion, for the chemical potential at the Fermi point and at strong coupling, the energetically preferred superconducting state is the uniaxial nematic state, which preserves time-reversal symmetry and provides a full (anisotropic) gap for quasiparticle excitations. In contrast, at a finite chemical potential, we find that the usual weak-coupling instability is towards the "cyclic state", well known from the studies of multicomponent Bose-Einstein condensates, which breaks time reversal symmetry maximally, has vanishing average value of angular momentum, and features 16 small Bogoliubov--Fermi surfaces. The Rarita-Schwinger-Weyl semimetals provide therefore the first example of weakly coupled, three-dimensional, isotropic d-wave superconductors where the ground state is uniquely determined by the quartic expansion of the mean-field free energy, and not afflicted by the accidental degeneracy first noticed by Mermin over 40 years ago. We discuss the appearance and stability of the Bogoliubov-Fermi surfaces in absence of inversion symmetry in the electronic Hamiltonian, as in the case at hand.

Spin-orbit coupling in wurtzite heterostructures

Effective spin-orbit (SO) Hamiltonians for conduction electrons in wurtzite heterostructures are lacking in the literature, in contrast to zincblende structures. Here we address this issue by deriving such an effective Hamiltonian valid for quantum wells, wires, and dots with arbitrary confining potentials and external magnetic fields. We start from an 8$\times$8 Kane model accounting for the $s$--$p_z$ orbital mixing important to wurtzite structures, but absent in zincblende, and apply both quasi-degenerate perturbation theory (L\"owdin partitioning) and the folding down approach to derive an effective 2$\times$2 electron Hamiltonian. We obtain the usual $k$-linear Rashba term arising from the structural inversion asymmetry of the wells and, differently from zincblende structures, a bulk Rashba-type term induced by the inversion asymmetry of the wurtzite lattice. We also find linear- and cubic-in-momentum Dresselhaus contributions. Both the bulk Rashba-type term and the Dresselhaus terms originate exclusively from the admixture of $s$- and $p_z$-like states in wurtzites structures. Interestingly, in these systems the linear Rashba and the Dresselhaus terms have the same symmetry and can in principle cancel each other out completely, thus making the spin a conserved quantity. We determine the intrasubband (intersubband) Rashba $\alpha_\nu$ ($\eta$) and linear Dresselhaus $\beta_\nu$ ($\Gamma$) SO strengths of GaN/AlGaN single and double wells with one and two occupied subbands ($\nu=1,2$). We believe our general effective Hamiltonian for electrons in wurtzite heterostructures put forward here, should stimulate additional theoretical works on wurtzite quantum wells, wires, and dots with variously defined geometries and external magnetic fields.

Measurement optimization in the variational quantum eigensolver using a minimum clique cover.

Solving the electronic structure problem using the Variational Quantum Eigensolver (VQE) technique involves the measurement of the Hamiltonian expectation value. The current hardware can perform only projective single-qubit measurements, and thus, the Hamiltonian expectation value is obtained by measuring parts of the Hamiltonian rather than the full Hamiltonian. This restriction makes the measurement process inefficient because the number of terms in the Hamiltonian grows as O(N4) with the size of the system, N. To optimize the VQE measurement, one can try to group as many Hamiltonian terms as possible for their simultaneous measurement. Single-qubit measurements allow one to group only the terms commuting within the corresponding single-qubit subspaces or qubit-wise commuting. We found that the qubit-wise commutativity between the Hamiltonian terms can be expressed as a graph and the problem of the optimal grouping is equivalent to finding a minimum clique cover (MCC) for the Hamiltonian graph. The MCC problem is NP-hard, but there exist several polynomial heuristic algorithms to solve it approximately. Several of these heuristics were tested in this work for a set of molecular electronic Hamiltonians. On average, grouping qubit-wise commuting terms reduced the number of operators to measure three times less compared to the total number of terms in the considered Hamiltonians.

Interplay of covalency, non-cubic crystal field, and spin-orbit coupling: A comparative study of [formula omitted], and [formula omitted] double perovskite iridates Sr2MIrO6 (M = Ce, Sc, Ca)

The interplay between various competing parameters, for example covalency, non-cubic crystal field, and spin-orbit coupling (SOC) leads to fascinating electronic and magnetic phases of matter. In the present work, the effect of these competing parameters on the ground state properties of the systems with d5,d4, and d3 electronic configurations are studied using atomic and two-site full multi-orbital man-body electronic Hamiltonian. In order to connect with the real world materials, explicit density functional calculations are employed to study the electronic and the magnetic properties of a series of double perovskite iridates Sr2MIrO6 (M = Ce, Sc, Ca) with formal valences of Ir: Ir4+ (d5), Ir5+ (d4), and Ir6+ (d3). All these iridates facilitate a finite noncubic crystal field and strong Ir-O covalency along with large SOC, thereby offering an excellent platform for the present study. Using the symmetry allowed magnetic structures, the magnetic properties of these materials are studied and compared with the available experimental results. The results of the present work are pertinent to describe the electronic properties of a broad family of spin-orbit coupled materials.

Exact solutions of a model for synthetic anyons in a noninteracting system

Synthetic anyons can be implemented in a noninteracting many-body system, by using specially tailored localized (physical) probes, which supply the demanded nontrivial topology in the system. We consider the Hamiltonian for noninteracting electrons in two-dimensions (2D), in a uniform magnetic field, where the probes are external solenoids with a magnetic flux that is a fraction of the flux quantum. The Hamiltonian could also be implemented in an ultracold (fermionic) atomic gas in 2D, in a uniform synthetic magnetic field, where the probes are lasers giving rise to synthetic solenoid gauge potentials. We find analytically and numerically the ground state of this system when only the lowest Landau level states are occupied. It is shown that the ground state is anyonic in the coordinates of the probes. We show that these synthetic anyons cannot be considered as emergent quasiparticles. The fusion rules of synthetic anyons are discussed for different microscopic realizations of the fusion process.

Středa formula for charge and spin currents

We consider a 2-dimensional Bloch–Landau–Pauli Hamiltonian for a spinful electron in a constant magnetic field subject to a periodic background potential. Assuming that the [Formula: see text]-component of the spin operator is conserved, we compute the linear response of the associated spin density of states to a small change in the magnetic field, and identify it with the spin Hall conductivity. This response is in the form of a spin Chern marker, which is in general quantized to a half-integer, and to an integer under the further assumption of time-reversal symmetry. Our result is thus a generalization to the context of the quantum spin Hall effect of the well-known formula by Středa, which is formulated instead for charge transport.

Measuring All Compatible Operators in One Series of Single-Qubit Measurements Using Unitary Transformations.

The Variational Quantum Eigensolver approach to the electronic structure problem on a quantum computer involves measurement of the Hamiltonian expectation value. Formally, quantum mechanics allows one to measure all mutually commuting or compatible operators simultaneously. Unfortunately, the current hardware permits measuring only a much more limited subset of operators that share a common tensor product eigen-basis. We introduce unitary transformations that transform any fully commuting group of operators to a group that can be measured on current hardware. These unitary operations can be encoded as a sequence of Clifford gates and let us not only measure much larger groups of terms but also to obtain these groups efficiently on a classical computer. The problem of finding the minimum number of fully commuting groups of terms covering the whole Hamiltonian is found to be equivalent to the minimum clique cover problem for a graph representing Hamiltonian terms as vertices and commutativity between them as edges. Tested on a set of molecular electronic Hamiltonians with up to 50 thousand terms, the introduced technique allows for the reduction of the number of separately measurable operator groups down to few hundreds, thus achieving up to 2 orders of magnitude reduction. Based on the test set results, the obtained gain scales at least linearly with the number of qubits.