Brillouin-Wigner Perturbation Theory Research Articles

Optimizing the regularization in size-consistent second-order Brillouin-Wigner perturbation theory.

Despite its simplicity and relatively low computational cost, second-order Møller-Plesset perturbation theory (MP2) is well-known to overbind noncovalent interactions between polarizable monomers and some organometallic bonds. In such situations, the pairwise-additive correlation energy expression in MP2 is inadequate. Although energy-gap dependent amplitude regularization can substantially improve the accuracy of conventional MP2 in these regimes, the same regularization parameter worsens the accuracy for small molecule thermochemistry and density-dependent properties. Recently, we proposed a repartitioning of Brillouin-Wigner perturbation theory that is size-consistent to second order (BW-s2), and a free parameter (α) was set to recover the exact dissociation limit of H2 in a minimal basis set. Alternatively α can be viewed as a regularization parameter, where each value of α represents a valid variant of BW-s2, which we denote as BW-s2(α). In this work, we semi-empirically optimize α for noncovalent interactions, thermochemistry, alkane conformational energies, electronic response properties, and transition metal datasets, leading to improvements in accuracy relative to the abinitio parameterization of BW-s2 and MP2. We demonstrate that the optimal α parameter (α = 4) is more transferable across chemical problems than energy-gap-dependent regularization parameters. This is attributable to the fact that the BW-s2(α) regularization strength depends on all of the information encoded in the t amplitudes rather than just orbital energy differences. While the computational scaling of BW-s2(α) is iterative O(N5), this effective and transferable approach to amplitude regularization is a promising route to incorporate higher-order correlation effects at second-order cost.

A Regularized Second-Order Correlation Method from Green's Function Theory.

We present a scalable single-particle framework to treat electronic correlation in molecules and materials motivated by Green's function theory. We derive a size-extensive Brillouin-Wigner perturbation theory from the single-particle Green's function by introducing the Goldstone self-energy. This new ground state correlation energy, referred to as Quasi-Particle MP2 theory (QPMP2), avoids the characteristic divergences present in both second-order Møller-Plesset perturbation theory and Coupled Cluster Singles and Doubles within the strongly correlated regime. We show that the exact ground state energy and properties of the Hubbard dimer are reproduced by QPMP2 and demonstrate the advantages of the approach for larger Hubbard models where the metal-to-insulator transition is qualitatively reproduced, contrasting with the complete failure of traditional methods. We apply this formalism to characteristic strongly correlated molecular systems and show that QPMP2 provides an efficient, size-consistent regularization of MP2.

Repartitioned Brillouin-Wigner perturbation theory with a size-consistent second-order correlation energy.

Second-order Møller-Plesset perturbation theory (MP2) often breaks down catastrophically in small-gap systems, leaving much to be desired in its performance for myriad chemical applications such as noncovalent interactions, thermochemistry, and dative bonding in transition metal complexes. This divergence problem has reignited interest in Brillouin-Wigner perturbation theory (BWPT), which is regular at all orders but lacks size consistency and extensivity, severely limiting its application to chemistry. In this work, we propose an alternative partitioning of the Hamiltonian that leads to a regular BWPT perturbation series that, through the second order, is size-extensive, size-consistent (provided its Hartree-Fock reference is also), and orbital invariant. Our second-order size-consistent Brillouin-Wigner (BW-s2) approach can describe the exact dissociation limit of H2 in a minimal basis set, regardless of the spin polarization of the reference orbitals. More broadly, we find that BW-s2 offers improvements relative to MP2 for covalent bond breaking, noncovalent interaction energies, and metal/organic reaction energies, although rivaling coupled-cluster with single and double substitutions for thermochemical properties.

On the iterative diagonalization of matrices in quantum chemistry: Reconciling preconditioner design with Brillouin-Wigner perturbation theory.

Iterative diagonalization of large matrices to search for a subset of eigenvalues that may be of interest has become routine throughout the field of quantum chemistry. Lanczos and Davidson algorithms hold a monopoly, in particular, owing to their excellent performance on diagonally dominant matrices. However, if the eigenvalues happen to be clustered inside overlapping Gershgorin disks, the convergence rate of both strategies can be noticeably degraded. In this work, we show how Davidson, Jacobi-Davidson, Lanczos, and preconditioned Lanczos correction vectors can be formulated using the reduced partitioning procedure, which takes advantage of the inherent flexibility promoted by Brillouin-Wigner perturbation (BW-PT) theory's resolvent operator. In doing so, we establish a connection between various preconditioning definitions and the BW-PT resolvent operator. Using Natural Localized Molecular Orbitals (NLMOs) to construct Configuration Interaction Singles (CIS) matrices, we study the impact the preconditioner choice has on the convergence rate for these comparatively dense matrices. We find that an attractive by-product of preconditioning the Lanczos algorithm is that the preconditioned variant only needs 21%-35% and 54%-61% of matrix-vector operations to extract the lowest energy solution of several Hartree-Fock- and NLMO-based CIS matrices, respectively. On the other hand, the standard Davidson preconditioning definition seems to be generally optimal in terms of requisite matrix-vector operations.

Note on the nonrelativistic TT¯ deformation

In this paper, we present our study on the $T\bar{T}$-deformation of non-relativistic complex scalar field theory. We find the closed form of the deformed Lagrangian by using the perturbation and the method of characteristics. Furthermore we compute the exact energy spectrum of the deformed free theory by using the Brillouin-Wigner perturbation theory in an appropriate regularization scheme.

Out of equilibrium chiral higher order topological insulator on a π -flux square lattice

One of the hallmarks of bulk topology is the existence of robust boundary localized states. For instance, a conventional d dimensional topological system hosts d − 1 dimensional surface modes, which are protected by non-spatial symmetries. Recently, this idea has been extended to higher order topological phases with boundary modes that are localized in lower dimensions such as in the corners or in one dimensional hinges of the system. In this work, we demonstrate that a higher order topological phase can be engineered in a nonequilibrium state when the time-independent model does not possess any symmetry protected topological states. The higher order topology is protected by an emerging chiral symmetry, which is generated through the Floquet driving. Using both the exact numerical method and an effective high-frequency Hamiltonian obtained from the Brillouin-Wigner (BW) perturbation theory, we verify the emerging topological phase on a π-flux square lattice. We show that the localized corner modes in our model are robust against a chiral symmetry preserving perturbation and can be classified as ‘extrinsic’ higher order topological phase. Finally, we identify a two dimensional topological invariant from the winding number of the corresponding sublattice symmetric one dimensional model. The latter model belongs to class AIII of ten-fold symmetry classification of topological matter.

A simplified account of the correlation effects to bond breaking processes: The Brillouin-Wigner perturbation theory using a multireference formulation

Adaptation of improved virtual orbital complete active space configuration interaction functions in state-specific multireference perturbation theory motivated by the Brillouin-Wigner perturbation scheme using Møller-Plesset multipartitioning is examined. The method, denoted as IVO-BWMRPT, focuses on only the root of principal interest at a time using single-root parameterization of Jeziorski-Monkhorst ansatz within the frame of an effective Hamiltonian. This approach yields size-extensive energy and avoids intruder-state problems in a natural manner. It allows relaxation of the reference space wave function in the presence of the perturbation which produces an important differential effect on the energy and cannot be neglected for quasidegenerate electronic states. The method has been tested against nontrivial situations such as the Be + H2 insertion profile along with the energy surfaces of FH and X2 (X = F, Cl, and Br), in which conventional single-reference methods generally fail, exhibiting very encouraging findings. We also consider the energy surfaces of ethylene (by breaking the π bond as well as the CC bond) and for the twisting of tetramethyleneethane. IVO-BWMRPT represents a rather balanced protocol for the description of molecules at a wide range of geometries, including stretched or dissociating bonds. Close agreement of our estimates with the reference values provides a useful measure for the success of the IVO-BWMRPT method to treat strongly correlated systems. Our results for TME show that the singlet state always lies below the triplet state for different conformations. The IVO-BWMRPT furnishes a compact and correct representation of the MR-wave function, and hence, a large variety of quasidegenerate situations can be accommodated within the method.

A Renormalized-Hamiltonian-Flow Approach to Eigenenergies and Eigenfunctions**Supported by the National Natural Science Foundation of China under Grant Nos. 11275179, 11535011, and 11775210

We introduce a decimation scheme of constructing renormalized Hamiltonian flows, which is useful in the study of properties of energy eigenfunctions, such as localization, as well as in approximate calculation of eigenenergies. The method is based on a generalized Brillouin-Wigner perturbation theory. Each flow is specific for a given energy and, at each step of the flow, a finite subspace of the Hilbert space is decimated in order to obtain a renormalized Hamiltonian for the next step. Eigenenergies of the original Hamiltonian appear as unstable fixed points of renormalized flows. Numerical illustration of the method is given in the Wigner-band random-matrix model.

Improving mean-field theory for bosons in optical lattices via degenerate perturbation theory

The objective of this paper is the theoretical description of the Mott-insulator to superfluid quantum phase transition of a Bose gas in an optical lattice. In former works the Rayleigh-Schr\"odinger perturbation theory was used within a mean-field approach, which yields partially non-physical results since the degeneracy between two adjacent Mott lobes is not taken into account. In order to correct such non-physical results we apply the Brillouin-Wigner perturbation theory to the mean-field approximation of the Bose-Hubbard model. Detailed explanations of how to use the Brillouin-Wigner theory are presented, including a graphical approach that allows to efficiently keep track of the respective analytic terms. To prove the validity of this computation, the results are compared with other works. Besides the analytic calculation of the phase boundary from Mott-insulator to superfluid phase, the condensate density is also determined by simultaneously solving two algebraic equations. The analytical and numerical results turn out to be physically meaningful and can cover a region of system parameters inaccessible until now. Our results are of particular interest provided an harmonic trap is added to the former calculations in an homogeneous system, in view of describing an experiment within the local density approximation. Thus, the paper represents an essential preparatory work for determining the experimentally observed wedding-cake structure of particle-density profile at both finite temperature and hopping.

Impact of high-frequency pumping on anomalous finite-size effects in three-dimensional topological insulators

Lowering of the thickness of a thin-film three-dimensional topological insulator down to a few nanometers results in the gap opening in the spectrum of topologically protected two-dimensional surface states. This phenomenon, which is referred to as the anomalous finite-size effect, originates from hybridization between the states propagating along the opposite boundaries. In this work, we consider a bismuth-based topological insulator and show how the coupling to an intense high-frequency linearly polarized pumping can further be used to manipulate the value of a gap. We address this effect within recently proposed Brillouin-Wigner perturbation theory that allows us to map a time-dependent problem into a stationary one. Our analysis reveals that both the gap and the components of the group velocity of the surface states can be tuned in a controllable fashion by adjusting the intensity of the driving field within an experimentally accessible range and demonstrate the effect of light-induced band inversion in the spectrum of the surface states for high enough values of the pump.

Behavior of the impurity atom in a weakly-interacting Bose gas

We studied the properties of a single impurity atom immersed in a dilute Bose condensate at low temperatures. In particular, we perturbatively obtained the momentum dependence of the impurity spectrum and damping. By means of the Brillouin-Wigner perturbation theory we also calculated the self-energy both for attractive and repulsive polaron in the long-wavelength limit. The stability problem of the impurity atom in a weakly-interacting Bose gas is also examined.

Brillouin-Wigner theory for Floquet topological phase transitions in spin-orbit-coupled materials

We develop the high frequency expansion based on the Brillouin-Wigner (B-W) perturbation theory for driven systems with spin-orbit coupling which is applicable to the cases of silicene, germanene and stanene. We compute the effective Hamiltonian in the zero photon subspace not only to order $O(\omega^{-1})$, but by keeping all the important terms to order $O(\omega^{-2})$, and obtain the photo-assisted correction terms to both the hopping and the spin-orbit terms, as well as new longer ranged hopping terms. We then use the effective static Hamiltonian to compute the phase diagram in the high frequency limit and compare it with the results of direct numerical computation of the Chern numbers of the Floquet bands, and show that at sufficiently large frequencies, the B-W theory high frequency expansion works well even in the presence of spin-orbit coupling terms.

Brillouin-Wigner theory for high-frequency expansion in periodically driven systems: Application to Floquet topological insulators

We construct a systematic high-frequency expansion for periodically driven quantum systems based on the Brillouin-Wigner (BW) perturbation theory, which generates an effective Hamiltonian on the projected zero-photon subspace in the Floquet theory, reproducing the quasienergies and eigenstates of the original Floquet Hamiltonian up to desired order in $1/\omega$, with $\omega$ being the frequency of the drive. The advantage of the BW method is that it is not only efficient in deriving higher-order terms, but even enables us to write down the whole infinite series expansion, as compared to the van Vleck degenerate perturbation theory. The expansion is also free from a spurious dependence on the driving phase, which has been an obstacle in the Floquet-Magnus expansion. We apply the BW expansion to various models of noninteracting electrons driven by circularly polarized light. As the amplitude of the light is increased, the system undergoes a series of Floquet topological-to-topological phase transitions, whose phase boundary in the high-frequency regime is well explained by the BW expansion. As the frequency is lowered, the high-frequency expansion breaks down at some point due to band touching with nonzero-photon sectors, where we find numerically even more intricate and richer Floquet topological phases spring out. We have then analyzed, with the Floquet dynamical mean-field theory, the effects of electron-electron interaction and energy dissipation. We have specifically revealed that phase transitions from Floquet-topological to Mott insulators emerge, where the phase boundaries can again be captured with the high-frequency expansion.

Molecular Application of a State Specific Multi-Reference Brillouin–Wigner Perturbation Theory**Supported by the Scientific and Technological Research Council of Turkey (TUBİTAK) under Grant No 2219-1/2013.

The single reference second order Brillouin–Wigner perturbation theory recently developed, which eliminates its size-extensivity error, has been generalized to state-specific, multi-reference (SS-MR), BWPT2 providing a size-extensive correction to the electron correlation problem for systems that demand the use of a multi-reference function. Illustrative numerical tests of the size-extensivity corrections are made for widely used molecules in their ground states, which are pronounced multi-reference characteristics. We have implemented two-reference and three-reference cases for CH2, BH and bond breaking process in the ground states of HF molecules. The results are compared with the rigorously size-extensive methods such as the Møller–Plesset perturbation theory, i.e., MP2, full configuration interaction (Full-CI) and allied methods using the same basis sets.

The pinning effect in a polar semiconductor quantum dot with Gaussian confinement: A study using the improved Wigner–Brillouin perturbation theory

The effect of electron–phonon interaction on a few low-lying energy levels in a polar semiconductor quantum dot with Gaussian confinement is studied by using an improved Wigner–Brillouin perturbation theory (IWBPT). In the absence of the electron–phonon interaction, the electronic ground state plus one phonon state is degenerate with the first excited electronic state plus the zero-phonon state at some value of the confinement length. Similarly, the electronic ground state plus one phonon state is also degenerate with the second excited electronic state plus the zero-phonon state at a larger value of the confinement length. It is shown that the electron–phonon interaction lifts these degeneracies and as a result, the excited state energy levels bend downward and get pinned to the ground state plus one phonon state as the confinement frequency is increased. Our calculations are finally applied to GaAs and InSb quantum dots.

Plasmons and their interaction with electrons in trilayer graphene

The interaction between electrons and plasmons in trilayer graphene is investigated within the Overhauser approach resulting in the 'plasmaron' quasi-particle. This interaction is cast into a field theoretical problem, nd its effect on the energy spectrum is calculated using improved Wigner-Brillouin perturbation theory. The plasmaron spectrum is shifted with respect to the bare electron spectrum by $\Delta E(\mathbf{k})\sim 50\div200\,{\rm meV}$ for ABC stacked trilayer graphene and for ABA trilayer graphene by $\Delta E(\mathbf{k})\sim 30\div150\,{\rm meV}$ ($\Delta E(\mathbf{k})\sim 1\div5\,{\rm meV}$) for the hyperbolic linear) part of the spectrum. The shift in general increases with the electron concentration $n_{e}$ and electron momentum. The dispersion of plasmarons is more pronounced in \textit{ABC} stacked than in ABA tacked trilayer graphene, because of the different energy band structure and their different plasmon dispersion.

A Variant of the Brillouin-Wigner Perturbation Theory with Epstein-Nesbet Partitioning

We present an elementary pedagogical derivation of the Brillouin-Wigner and the Rayleigh-Schr<TEX>$\ddot{o}$</TEX>dinger perturbation theories with Epstein-Nesbet partitioning. A variant of the Brillouin-Wigner perturbation theory is also introduced, which can be easily extended to the quasi-degenerate case. A main advantage of the new theory is that the computing time required for obtaining the successive higher-order results is minimal after the third-order calculation. We illustrate the accuracy of the new perturbation theory for some simple model systems like the perturbed harmonic oscillator and the particle in a box.

Resonant dipole–dipole interaction in confined and strong-coupling dielectric geometries

Using the electromagnetic response function of an electric dipole located within a dielectric geometry, we derive the mathematical equivalence between the classical response and quantum mechanical resonant dipole–dipole interaction between two quantum objects (atoms, quantum dots, etc). Cooperative spontaneous emission likewise emerges from this equivalence. We introduce a practical numerical technique using finite difference time domain for calculating both dipole–dipole interaction and collective spontaneous emission in confined dielectric structures, where strong light–matter coupling might arise. This method is capable of obtaining resonant dipole–dipole interaction over a wide range of frequencies in a single run. Our method recaptures the results of quantum mechanical second order perturbation theory for weak light–matter coupling. In strong coupling situations such as near a photonic band edge, second order Rayleigh–Schrödinger perturbation theory leads to divergences, and instead Brillouin–Wigner perturbation theory is required. This is equivalent to the use of a variational wavefunction to describe the exciton transfer between initial and final states. We introduce a system of coupled classical oscillators, that describes resonant dipole–dipole interaction and vacuum Rabi splitting in the strong-coupling regime, and that provides an effective numerical scheme based on the finite difference time domain method. This includes the effects of quantum entanglement and the correlation of quantum fluctuations. We discuss the crossover to Forster energy transfer when quantum correlations between the dipoles are damped by strong environmental interactions.

An alternative approximation to state-specific multireference second-order Brillouin-Wigner perturbation theory: size-extensivity correction

State-specific, multireference, second order, Brillouin-Wigner perturbation theory is examined provided that providing a size-extensive correction to the electron correlation problem for systems that demand the use of a multireference function. We derived the renormalization term. An important aspect of this renormalization term is to cancel the non-physical terms. The computer implementations are made for bond breaking process in the ground states of the diatomic hydride using the two configuration state functions. We have achieved improved results. The results are compared with the rigorously size-extensive methods such as, MOller-Plesset perturbation theory, that is, MP2, full configuration interaction and allied methods using the same basis sets.

Second-order Brillouin-Wigner perturbation theory: size-extensivity correction

Size-extensivity correction to second-order Brillouin-Wigner perturbation theory is derived and implemented. For the size-extensivity correction, renormalization term is obtained by modifying the non-physical term in the denominator of the second-order Brillouin-Wigner formulae. We have achieved improved results. The method is illustrated in a series calculations on H2O, BH, HOF, Be and Ne using three different basis sets, and the results are then compared with corresponding coupled cluster double and second-order MOller–Plesset perturbation theory.