Effective Hamiltonian Theory Research Articles

Bath-induced interactions and transient dynamics in open quantum systems at strong coupling: Effective Hamiltonian approach.

Understanding the dynamics of dissipative quantum systems, particularly beyond the weak coupling approximation, is central to various quantum applications. While numerically exact methods provide accurate solutions, they often lack the analytical insight provided by theoretical approaches. In this study, we employ the recently developed method dubbed the effective Hamiltonian theory to understand the dynamics of system-bath configurations without resorting to a perturbative description of the system-bath coupling energy. Through a combination of mapping steps and truncation, the effective Hamiltonian theory offers both analytical insights into signatures of strong couplings in open quantum systems and a straightforward path for numerical simulations. To validate the accuracy of the method, we apply it to two canonical models: a single spin immersed in a bosonic bath and two noninteracting spins in a common bath. In both cases, we study the transient regime and the steady state limit at nonzero temperature and spanning system-bath interactions from the weak to the strong regime. By comparing the results of the effective Hamiltonian theory with numerically exact simulations, we show that although the former overlooks non-Markovian features in the transient equilibration dynamics, it correctly captures non-perturbative bath-generated couplings between otherwise non-interacting spins, as observed in their synchronization dynamics and correlations. Altogether, the effective Hamiltonian theory offers a powerful approach for understanding strong coupling dynamics and thermodynamics, capturing the signatures of such interactions in both relaxation dynamics and in the steady state limit.

A two-step Rayleigh-Schrödinger Brillouin-Wigner approach to transition energies

Perturbative methods are attractive to describe the electronic structure of molecular systems because of their low-computational cost and systematically improvable character. In this work, a two-step perturbative approach is introduced combining multi-state Rayleigh-Schrödinger (effective Hamiltonian theory) and state-specific Brillouin-Wigner schemes to treat degenerate configurations and yield an efficient evaluation of multiple energies. The first step produces model functions and an updated definition of the perturbative partitioning of the Hamiltonian. The second step inherits the improved starting point provided in the first step, enabling then faster processing of the perturbative corrections for each individual state. The here-proposed two-step method is exemplified on a model-Hamiltonian of increasing complexity.

Effective Hamiltonian theory: An approximation to the equilibrium state of open quantum systems

Effective Hamiltonian theory: An approximation to the equilibrium state of open quantum systems

Effective-Hamiltonian Theory of Open Quantum Systems at Strong Coupling

A new technique for open quantum dynamics, combining reaction coordinate mappings and the polaron transform, allows for efficient description of strong system-bath couplings, opening the way for novel applications in nanoscale transport and thermodynamics.

Solving Anderson Impurity Model by the Effective Hamiltonian Theory

We apply the Self-Consistent Effective Hamiltonian Theory (SCEHT), which uses a general variational Fermionic many-body wave function to generate an effective Hamiltonian in a quadratic form, to the Anderson impurity model. The chiral symmetry-breaking quadratic effective Hamiltonian is solved exactly for the single Fermion excitation spectrum. We validate the theory by numerically solving a model problem. The solution shows the correct Kondo resonance in the quasi-particle density of states.

Block Effective Hamiltonian Theory and Its Application.

Block effective Hamiltonian theory (BEHT) is presented in this work. Configuration interaction functions are divided into P, Q, and R spaces. Effective Hamiltonian is constructed with the partitioning technique within the P space. The eigenvalue problem of the effective Hamiltonian is then solved iteratively. It is demonstrated that the ground-state energies of N2, HF, and F2 calculated with BEHT converge to the multireference configuration interaction energies from below and the iteration number becomes smaller as BEHT energy becomes closer to the exact energy. The accuracy of BEHT is better than that of the second-order multireference perturbation theory, although the matrix elements in both methods are the same. The ionization potentials of the singlet state of HF, the doublet state of F, and the triplet state of NH and the potential energy curves of CH4, C2, and N2 are calculated with BEHT and compared with experiments and results of CASSCF, CCSD, and CCSD(T) and the results of the full configuration interaction if available. The iteration numbers are all less than 10 in this study. These calculations show the good performances of BEHT in comparison with other theoretical approximation methods.

Designing broadband pulsed dynamic nuclear polarization sequences in static solids.

Dynamic nuclear polarization (DNP) is a nuclear magnetic resonance (NMR) hyperpolarization technique that mediates polarization transfer from unpaired electrons with large thermal polarization to NMR-active nuclei via microwave (mw) irradiation. The ability to generate arbitrarily shaped mw pulses using arbitrary waveform generators allows for remarkable improvement of the robustness and versatility of DNP. We present here novel design principles based on single-spin vector effective Hamiltonian theory to develop new broadband DNP pulse sequences, namely, an adiabatic version of XiX (X–inverse X)–DNP and a broadband excitation by amplitude modulation (BEAM)–DNP experiment. We demonstrate that the adiabatic BEAM-DNP pulse sequence may achieve a 1H enhancement factor of ∼360, which is better than ramped-amplitude NOVEL (nuclear spin orientation via electron spin locking) at ∼0.35 T and 80 K in static solids doped with trityl radicals. In addition, the bandwidth of the BEAM-DNP experiments (~50 MHz) is about three times the 1H Larmor frequency. The generality of our theoretical approach will be helpful in the development of new pulsed DNP sequences.

Accurate analysis and perspectives for systematic design of magnetic resonance experiments using single-spin vector and exact effective Hamiltonian theory

Aimed at fundamental understanding and design of advanced magnetic resonance experiments on basis of Hamiltonians, we describe highly convergent and exact effective Hamiltonian methods which alleviate important deficits of current less accurate methods. This involves single-spin vector effective Hamiltonian theory (SSV-EHT) to first order in the interaction frame of rf and chemical shift offsets as well as exact effective Hamiltonian theory (EEHT) being an exact approach to average Hamiltonian theory not relying on interaction frame transformations. Bringing these methods together, we present tools to analyze challenging experiments in need of considering large static components in Hamiltonian (e.g., offsets) while economizing with radiofrequency irradiation power. It is demonstrated how the two complementary tools may provide important new insight into the detailed effective Hamiltonians of advanced NMR experiments, noting that the methods are by no means restricted to NMR. This is demonstrated for isotropic mixing in liquid-state NMR and dipolar recoupling in solid-state NMR where insight into the delicate interplay between bilinear two-spin and linear single-spin terms in the effective Hamiltonian may increase understanding of determinants for broadband excitation and the formation of recoupling resonances. Furthermore, we demonstrate how simple products single-spin effective Hamiltonians may be used as generators of multiple-spin effective Hamiltonians and though this a new approach to density operator calculations for large multiple-spin systems.

Anyon condensation: coherent states, symmetry enriched topological phases, Goldstone theorem, and dynamical rearrangement of symmetry

Although the mathematics of anyon condensation in topological phases has been studied intensively in recent years, a proof of its physical existence is tantamount to constructing an effective Hamiltonian theory. In this paper, we concretely establish the physical foundation of anyon condensation by building the effective Hamiltonian and the Hilbert space, in which we explicitly construct the vacuum of the condensed phase as the coherent states that are the eigenstates of the creation operators creating the condensate anyons. Along with this construction, which is analogous to Laughlin’s construction of wavefunctions of fractional quantum hall states, we generalize the Goldstone theorem in the usual spontaneous symmetry breaking paradigm to the case of anyon condensation. We then prove that the condensed phase is a symmetry enriched (protected) topological phase by directly constructing the corresponding symmetry transformations, which can be considered as a generalization of the Bogoliubov transformation.

Effective Hamiltonians for almost-periodically driven quantum systems* *Contribution to the special collection ‘Koopman methods in classical and quantum-classical mechanics’

We present an effective Hamiltonian theory available for some quasi-periodically driven quantum systems which does not need the knowledge of the Fourier frequencies of the control signal. It could also be available for some chaotically driven quantum systems. It is based on the Koopman approach which generalizes the Floquet approach used with periodically driven systems. We show the properties of the quasi-energy states (eigenvectors of the effective Hamiltonian) as quasi-recurrent states of the quantum system.

Topological electronic states and thermoelectric transport at phase boundaries in single-layer WSe2: an effective Hamiltonian theory

Monolayer transition metal dichalcogenides in the distorted octahedral 1T′ phase exhibit a large bulk bandgap and gapless boundary states, which is an asset in the ongoing quest for topological electronics. In single-layer tungsten diselenide (WSe2), the boundary states have been observed at well ordered interfaces between 1T′ and semiconducting (1H) phases. This paper proposes an effective 4-band theory for the boundary states in single-layer WSe2, describing a Kramers pair of in-gap states as well as the behaviour at the spectrum termination points on the conduction and valence bands of the 1T′ phase. The spectrum termination points determine the temperature and chemical potential dependences of the ballistic conductance and thermopower at the phase boundary. Notably, the thermopower shows an ambipolar behaviour, changing the sign in the bandgap of the 1T′–WSe2 and reflecting its particle-hole asymmetry. The theory establishes a link between the bulk band structure and ballistic boundary transport in single-layer WSe2 and is applicable to a range of related topological materials.

Evaluating first-order molecular properties of delocalized ionic or excited states in molecular aggregates by renormalized excitonic method

In the past few years, the renormalized excitonic model (REM) approach was developed as an efficient low-scaling ab initio excited state method, which assumes the low-lying excited states of the whole system are a linear combination of various single monomer excitations and utilizes the effective Hamiltonian theory to derive their couplings. In this work, we further extend the REM calculations for the evaluations of first-order molecular properties (e.g. charge population and transition dipole moment) of delocalized ionic or excited states in molecular aggregates, through generalizing the effective Hamiltonian theory to effective operator representation. Results from the test calculations for four different kinds of one dimensional (1D) molecular aggregates (ammonia, formaldehyde, ethylene and pyrrole) indicate that our new scheme can efficiently describe not only the energies but also wavefunction properties of the low-lying delocalized electronic states in large systems.

Self-consistent effective Hamiltonian theory for fermionic many-body systems

Using a separable many-body variational wavefunction, we formulate a self-consistent effective Hamiltonian theory for fermionic many-body system. The theory is applied to the two-dimensional (2D) Hubbard model as an example to demonstrate its capability and computational effectiveness. Most remarkably for the Hubbard model in 2D, a highly unconventional quadruple-fermion non-Cooper pair order parameter is discovered.

Effective Hamiltonian theory of the geometric evolution of quantum systems

In this work we present an effective Hamiltonian description of the quantum dynamics of a generalized Lambda system undergoing adiabatic evolution. We assume the system to be initialized in the dark subspace and show that its holonomic evolution can be viewed as a conventional Hamiltonian dynamics in an appropriately chosen extended Hilbert space. In contrast to the existing approaches, our method does not require the calculation of the non-Abelian Berry connection and can be applied without any parametrization of the dark subspace, which becomes a challenging problem with increasing system size.

Multiphoton process in cavity QED photons for implementing a three-qubit quantum gate operation

Based on cavity QED of free atoms, we theoretically investigate the implementation of a three-qubit quantum phase gate in which the three qubits are represented by the photons in modes of the cavity. A single four-level atom in double-V type passing through the high-Q cavity is used to implement the gate. We apply the theory of multiphoton resonance and use two-level effective Hamiltonians to predict the proper values for detunings, coupling constants, and interaction times. By the use of both the density matrix approach and wave function method, the influence of the decoherence processes is theoretically and numerically analyzed. Further, we address the effects of deviation in detunings and coupling coefficients and find that the gate operation is substantially insensitive to such variations. Finally, we show that the proposed scheme here can be extended for the implementation of multiqubit quantum phase gates.

Nonperturbative theory of effective Hamiltonians for deformations in two-dimensional materials: Moiré systems and dislocations

We provide a method for the generation of effective continuum Hamiltonians that goes beyond the well known k.p method in being equally effective in both high, and low (or no) symmetry situations. Our approach is based on a surprising exact map of the two-centre tight-binding method onto a compact continuum Hamiltonian, with a precise condition given for the hermiticity of the latter object. We apply this method to a broad range of low dimensional systems of both high and low symmetry: graphene, graphdiyne, {\gamma}-graphyne, 6,6,12-graphyne, twist bilayer graphene, and partial dislocation networks in Bernal stacked bilayer graphene. For the single layer systems the method yields Hamiltonians for the ideal lattices, as well as a systematic theory for corrections due to deformation. In the case of bilayer graphene we provide a compact expression for an effective field capable of describing any stacking deformation of the bilayer; twist bilayer graphene, as well as the partial dislocation network in AB stacked graphene, emerge as special cases of this field. For the latter system we find (i) charge pooling on the mosaic of AB and AC segments near the Dirac point and (ii) localized current carrying states on the partials with the current density characterized by both intralayer and interlayer components.

Theoretical study of the LiNa molecule beyond the Born–Oppenheimer approximation: adiabatic and diabatic potential energy curves, radial coupling, adiabatic correction, dipole moments and vibrational levels

ABSTRACTThe adiabatic potential energy curves for ground and many excited states of 1, 3Σ+, 1,3Π, 1,3Δ symmetries of the LiNa molecule have been performed. We have used an ab initio approach based on non-empirical pseudopotentials, parameterised l-dependent polarisation potentials and full configuration interaction calculations. In addition, the adiabatic potential energy curves determined in our previous work [Mabrouk and Berriche, J. Phys. B: At. Mol. Opt. Phys. 41, 155101 (2008).] are corrected by using a diabatisation procedure, based on the effective Hamiltonian theory and an effective metric. The diabatic permanent moments for first 10 1Σ+ electronic states show linear behaviours, especially at intermediate and large distance. The transition dipole moment between neighbour states has revealed many peaks located around the avoided crossing positions. The radial coupling between the adiabatic states was calculated using the Hellmann-Feynman formula and numerical differentiation of the rotation matrix. The first and the second derivatives revealed many peaks, associated to neutral-neutral and ionic-neutral crossings. Furthermore, the radial coupling is used to evaluate the adiabatic correction, which is found to be of an order of tens and hundreds of cm−1, especially of higher excited states. In addition, we have determined the vibrational level spacing for all studied states.

Hubbard Trimer with Spin–Orbit Coupling: Hartree–Fock Solutions, (Non)Collinearity, and Anisotropic Spin Hamiltonian

We present unrestricted and generalized Hartree-Fock solutions (UHF and GHF, respectively) for the single-band Hubbard model of an equilateral triangle. Spin-orbit coupling (SOC) is treated self-consistently, and HF stability and properties of different spin structures are studied in detail. The GHF solution switches from noncollinear to collinear when crossing a high-symmetry point in parameter space (spanned by the amplitudes of spin-conserving and spin-dependent hopping, i.e., kinetic energy and SOC, respectively). The collinear GHF solution represents a simple example to disprove the notion that a collinear vector spin density in a Slater determinant necessarily entails a defined spin projection. Spin Hamiltonian parameters for the anisotropic interaction between three spin-1/2 centers are extracted from HF energies and subsequently compared to exact results from effective Hamiltonian theory. This provides an unambiguous benchmark for interpreting broken-symmetry mean-field solutions in terms of spin configurations and puts this semiclassical approach (frequently applied in broken-symmetry density functional theory) on a firmer basis.

Adiabatic and Diabatic Investigation of Numerous Electronic States for the Alkali Dimer FrNa.

The current paper reports a global investigation of all excited states below the ionic limit Fr+Na- of FrNa molecule following diabatic and adiabatic representations. The adiabatic and diabatic potential energy curves (PECs) for Σ+, Π, and Δ symmetries have been calculated for a dense grid of internuclear distances. The transition and permanent dipole moments (TDM and PDM) have been reported for both representations. Regarding the pseudopotential approach and full valence configuration interaction (FCI), the ab initio computation has been performed. Furthermore, the diabatization method was achieved by the use of the variational effective Hamiltonian theory (VEH). This latter served to assess the nonadiabatic coupling between the treated adiabatic states and to eliminate it employing a suitable unitary transformation matrix. The detailed computation of the PECs and PDM and TDM curves of the ground and excited states play a key role to coordinate experimental efforts in order to create cold and ultracold molecules in their ground stable rovibrational levels.

Exact Mapping from Many-Spin Hamiltonians to Giant-Spin Hamiltonians.

Thermodynamic and spectroscopic data of exchange-coupled molecular spin clusters (e.g. single-molecule magnets) are routinely interpreted in terms of two different models: the many-spin Hamiltonian (MSH) explicitly considers couplings between individual spin centers, while the giant-spin Hamiltonian (GSH) treats the system as a single collective spin. When isotropic exchange coupling is weak, the physical compatibility between both spin Hamiltonian models becomes a serious concern, due to mixing of spin multiplets by local zero-field splitting (ZFS) interactions ('S-mixing'). Until now, this effect, which makes the mapping MSH→GSH ('spin projection') non-trivial, had only been treated perturbationally (up to third order), with obvious limitations. Here, based on exact diagonalization of the MSH, canonical effective Hamiltonian theory is applied to construct a GSH that exactly matches the energies of the relevant (2S+1) states comprising an effective spin multiplet. For comparison, a recently developed strategy for the unique derivation of effective ('pseudospin') Hamiltonians, now routinely employed in ab initio calculations of mononuclear systems, is adapted to the problem of spin projection. Expansion of the zero-field Hamiltonian and the magnetic moment in terms of irreducible tensor operators (or Stevens operators) yields terms of all ranks k (up to k=2S) in the effective spin. Calculations employing published MSH parameters illustrate exact spin projection for the well-investigated [Ni(hmp)(dmb)Cl]4 ('Ni4 ') single-molecule magnet, which displays weak isotropic exchange (dmb=3,3-dimethyl-1-butanol, hmp- is the anion of 2-hydroxymethylpyridine). The performance of the resulting GSH in finite field is assessed in terms of EPR resonances and diabolical points. The large tunnel splitting in the M=± 4 ground doublet of the S=4 multiplet, responsible for fast tunneling in Ni4 , is attributed to a Stevens operator with eightfold rotational symmetry, marking the first quantification of a k=8 term in a spin cluster. The unique and exact mapping MSH→GSH should be of general importance for weakly-coupled systems; it represents a mandatory ultimate step for comparing theoretical predictions (e.g. from quantum-chemical calculations) to ZFS, hyperfine or g-tensors from spectral fittings.