Separable Hamiltonian Research Articles

The effects of vacancy ordering on diffusion: a statistical study

In this paper we investigate the interconnection between vacancy-ordered phases and vacancy self-diffusion. Here, we investigate three ordered phases on a square lattice with energetics defined by two separate Hamiltonians. In the first case we used a classical antiferromagnetic Ising model Hamiltonian in order to generate a 'checkerboard' type ordered structure. In the second case, we used a modified Ising model with competing influence of second and third nearest-neighbors, which resulted in both 'hatch' and 'labyrinthine' structures, depending on concentration. To understand how vacancy-ordering affects diffusion, we determined the tracer diffusivity using rejection-free kinetic Monte Carlo and compared disordered and ordered structures. Finally, we developed an analytical model describing diffusion in the ordered 'checkerboard' structure and found that it was able to predict apparent activation energies in the ordered and disordered structures. Our results suggest that it is short-range order rather than long-range order that most significantly affects tracer diffusion.

Separable graph Hamiltonian network: A graph deep learning model for lattice systems

Addressing the challenges posed by nonlinear lattice models, which are vital across diverse scientific disciplines, we present a new deep learning approach that harnesses the power of graph neural networks. By representing the lattice system as a graph and leveraging the graph structures to identify complex nonlinear relationships, we have developed a flexible solution that outperforms traditional techniques. Our model not only offers precise trajectory predictions and energy conservation properties by incorporating separable Hamiltonians but also proves superior to existing top-tier models when tested on classic nonlinear oscillator lattice problems: a mixed Fermi-Pasta-Ulam Klein-Gordon, a Klein-Gordon system with long-range interactions, and a two-dimensional Frenkel-Kontorova, highlighting its potential for wide-reaching applications. Published by the American Physical Society 2024

An efficient method of finding new symplectic schemes for Hamiltonian mechanics problems with the aid of parametric Gröbner bases

The explicit symplectic difference schemes are considered for the numerical solution of molecular dynamics problems described by systems with separable Hamiltonians. A general method for finding symplectic schemes of high order of accuracy using parametric Gröbner bases, resultants, permutations of variables, and optimization techniques is proposed. The implementation of the method is described by the example of four-stage partitioned Runge–Kutta (PRK) schemes of the Forest–Ruth and Yoshida families. 97 new PRK schemes of Forest–Ruth family have been obtained. The error functionals for five new schemes FR47, FR50, FR51, FR52, and FR59 are smaller by more than two orders of magnitude than in the case of the fourth-order schemes, which were obtained previously in the explicit form in this family. In the family of Yoshida schemes, 115 new schemes have been found. Verification of the schemes was carried out on the Kepler's problem, which has the exact solution. Calculations of this task performed at large time steps showed that the FR50 scheme significantly exceeds in terms of accuracy the four-stage Forest–Ruth schemes known in the literature, the Verlet scheme, schemes from the Yoshida family Y7, Y95, Y110, and a six-stage fourth-order scheme.

Contrasting the Implicit Method in Incoherent Lagrangian and the Correction Map Method in Hamiltonian

The equations of motion for a Lagrangian mainly refer to the acceleration equations, which can be obtained by the Euler–Lagrange equations. In the post-Newtonian Lagrangian form of general relativity, the Lagrangian systems can only maintain a certain post-Newtonian order and are incoherent Lagrangians since the higher-order terms are omitted. This truncation can cause some changes in the constant of motion. However, in celestial mechanics, Hamiltonians are more commonly used than Lagrangians. The conversion from Lagrangianto Hamiltonian can be achieved through the Legendre transformation. The coordinate momentum separable Hamiltonian can be computed by the symplectic algorithm, whereas the inseparable Hamiltonian can be used to compute the evolution of motion by the phase-space expansion method. Our recent work involves the design of a multi-factor correction map for the phase-space expansion method, known as the correction map method. In this paper, we compare the performance of the implicit algorithm in post-Newtonian Lagrangians and the correction map method in post-Newtonian Hamiltonians. Specifically, we investigate the extent to which both methods can uphold invariance of the motion’s constants, such as energy conservation and angular momentum preservation. Ultimately, the results of numerical simulations demonstrate the superior performance of the correction map method, particularly with respect to angular momentum conservation.

Explicit K-Symplectic and Symplectic-like Methods for Charged Particle System in General Magnetic Field

We propose explicit K-symplectic and explicit symplectic-like methods for the charged particle system in a general strong magnetic field. The K-symplectic methods are also symmetric. The charged particle system can be expressed both in a canonical and a non-canonical Hamiltonian system. If the three components of the magnetic field can be integrated in closed forms, we construct explicit K-symplectic methods for the non-canonical charged particle system; otherwise, explicit symplectic-like methods can be constructed for the canonical charged particle system. The symplectic-like methods are constructed by extending the original phase space and obtaining the augmented separable Hamiltonian, and then by using the splitting method and the midpoint permutation. The numerical experiments have shown that compared with the higher order implicit Runge-Kutta method, the explicit K-symplectic and explicit symplectic-like methods have obvious advantages in long-term energy conservation and higher computational efficiency. It is also shown that the influence of the parameter ε in the general strong magnetic field on the Runge-Kutta method is bigger than the two kinds of symplectic methods.

Bregman dynamics, contact transformations and convex optimization

Recent research on accelerated gradient methods of use in optimization has demonstrated that these methods can be derived as discretizations of dynamical systems. This, in turn, has provided a basis for more systematic investigations, especially into the geometric structure of those dynamical systems and their structure-preserving discretizations. In this work, we introduce dynamical systems defined through a contact geometry which are not only naturally suited to the optimization goal but also subsume all previous methods based on geometric dynamical systems. As a consequence, all the deterministic flows used in optimization share an extremely interesting geometric property: they are invariant under contact transformations. In our main result, we exploit this observation to show that the celebrated Bregman Hamiltonian system can always be transformed into an equivalent but separable Hamiltonian by means of a contact transformation. This in turn enables the development of fast and robust discretizations through geometric contact splitting integrators. As an illustration, we propose the Relativistic Bregman algorithm, and show in some paradigmatic examples that it compares favorably with respect to standard optimization algorithms such as classical momentum and Nesterov’s accelerated gradient.

Absorption band structure of the photochromic dimethyldihydropyrene/metacyclophanediene couple. Insight from vibronic coupling theory.

A detailed insight behind the structure of absorption bands of the photochromic couple dimethyldihydropyrene (DHP)/metacyclophanediene (CPD) is studied employing vibronic coupling theory. Two separate model molecular Hamiltonians, including a maximum of four electronic states and 18 vibrational modes for DHP and five electronic states and 20 vibrational modes for CPD, are constructed in a diabatic electronic representation. The parameters of the Hamiltonians are estimated from the electronic energies obtained from extensive density functional theory (DFT) and time-dependent DFT calculations. Based on these Hamiltonians' parameters, a detailed analysis of potential energy curves is performed in conjunction with positional and energetic locations of several stationary points in multi-dimensional potential energy surfaces. Based on the results of electronic structure calculations, quantum nuclear dynamics studies on the electronic excited states of DHP and CPD are performed to understand the impact of non-adiabatic effects on the formation of vibronic structures of absorption bands of these photo-isomers.

On the conservative character of discretizations to Itô-Hamiltonian systems with small noise

In this paper, we consider stochastic Hamiltonian systems of Itô type driven by a multiplicative small noise. It is well-known, indeed, that stochastic Hamiltonian problems are suitable candidates to reconcile the Hamiltonian classical mechanics with the non-differentiability of the Wiener process, which provides the innovative character of stochastic effects. In particular, in this work, we provide a characterization of the behavior of averaged Hamiltonians arised in such systems, with more emphasis on the separable and quadratic Hamiltonians. Next, we show that, in general, first order approximations to such systems are not able to retain the same behavior discovered for the exact averaged Hamiltonian. Hence, the analysis for the specific case of ϑ-methods is performed. Finally, numerical evidence is depicted in order to confirm theoretical results.

Non-Hermitian skin effect in two dimensional continuous systems

An extensive number of the eigenstates can become exponentially localized at one boundary of nonreciprocal non-Hermitian systems. This effect is known as the non-Hermitian skin effect and has been studied mostly in tight-binding lattices. To extend the skin effect to continues systems beyond 1D, we introduce a quadratic imaginary vector potential in the continuous two dimensional Schrödinger equation. We find that inseparable eigenfunctions for separable nonreciprocal Hamiltonians appear under infinite boundary conditions. Introducing boundaries destroy them and hence they can only be used as quasi-stationary states in practice. We show that all eigenstates can be clustered at the point where the imaginary vector potential is minimum in a confined system.

Orbital Flips Caused by the Eccentric Von Zeipel–Lidov–Kozai Effect in Nonrestricted Hierarchical Planetary Systems

The eccentric von Zeipel–Lidov–Kozai effect is widely applied to diverse astrophysical settings. In the restricted hierarchical three-body system, the topic of orbital flips has been extensively studied. However, it is far from being understood for nonrestricted circumstances. In this work, the dynamics of orbital flips are investigated under the Hamiltonian model at the octupole-level approximation for nonrestricted hierarchical planetary systems, where the outer planet is more massive than the inner one. Numerical distribution of flipping orbits shows that there are three major flipping regions, distributed in low-, intermediate-, and high-eccentricity spaces. Poincaré sections indicate that those islands of libration centered near i tot = 90° can lead to orbital flips. Thus, we refer to the behavior of orbital flips as a resonance phenomenon. From this viewpoint, dynamical models of orbital flips can be described by a separable Hamiltonian, which can be treated by a means of perturbation theory. The resonant model for orbital flips is formulated based on the adiabatic invariant approximation and then phase portraits are generated by plotting level curves of adiabatic invariants with the given Hamiltonian. By analyzing phase portraits, analytical boundaries of libration and circulation zones causing orbital flips are obtained. As expected, the numerical and analytical conditions that allow orbits to flip agree well with each other. The phenomenon of orbital flips in nonrestricted hierarchical problems can be well understood with the help of dynamical structures of secular resonance.

Mean field games master equations with nonseparable Hamiltonians and displacement monotonicity

In this manuscript we propose a structural condition on nonseparable Hamiltonians, which we term displacement monotonicity condition, to study second-order mean field games master equations. A rate of dissipation of a bilinear form is brought to bear a global (in time) well-posedness theory, based on a priori uniform Lipschitz estimates on the solution in the measure variable. Displacement monotonicity being sometimes in dichotomy with the widely used Lasry–Lions monotonicity condition, the novelties of this work persist even when restricted to separable Hamiltonians.

Fourier Transform, Dirac Commutator, Energy Conservation, and Correspondence Principle for Electrical Engineers

The canonical commutation relation is a fundamental postulate of the quantum theory regarding the operators needed in quantum description of physical observables. It is shown that the Fourier transform is derivable from this seemingly simple postulate along with the basic properties of the position and momentum operators. Further discussions on the canonical commutation relation reveal its connection to a more fundamental notion that energy must be conserved. This discussion also unveils the mathematical homomorphism between the classical and quantum theories for systems represented by sum separable Hamiltonians. Another link between the classical and quantum theories is established by the correspondence principle which states that the classical theory emerges from quantum theory in the limit of vanishingly small Planck constant. Finally, the quantum Maxwell’s equations, which have been derived in our previous works, are presented and briefly discussed, and the 3-D mode transform is derived that can be interpreted as a generalization of the Fourier transform. We present both the details and meanings of the 3-D mode transform which will serve as a foundation for a full 3-D quantum finite-difference time-domain method.

Higher-order symplectic integration techniques for molecular dynamics problems

The explicit symplectic difference schemes with a number of stages from 1 to 5 are considered for the numerical solution of molecular dynamics problems described by systems with separable Hamiltonians. A general method for finding symplectic schemes of high order of accuracy using Gröbner bases is proposed. It is shown that it is possible to significantly increase the accuracy of symplectic schemes without increasing the number of stages by obtaining all possible real schemes with the aid of Gröbner bases. For the numbers of stages 2, 3, and 4, the parameters of Runge–Kutta–Nyström (RKN) schemes and partitioned Runge–Kutta (PRK) schemes are obtained using the Gröbner basis technique. It is shown that there exists only one explicit invertible (symmetric) two-stage RKN scheme. In the cases of the vanishing Vandermonde determinant, 20 new real four-stage RKN schemes and 18 new PRK schemes of Forest–Ruth and Yoshida were found in the analytic form with the aid of Gröbner bases. In the cases of the nonzero Vandermonde determinant, four symmetric four-stage RKN schemes were derived in the analytic form with the aid of the Gröbner basis technique. In addition, for the number of stages 4 and 5, new nonsymmetric schemes were found using the Nelder–Mead numerical optimization method. In particular, four new schemes were obtained for the number of stages 4. For the number of stages 5, three new schemes were obtained in addition to four schemes known earlier. For each specific number of stages, a scheme has been found that is the best in terms of the minimum of the leading term of the approximation error. The relations have been established between the polynomials entering the expansions of the errors of each scheme for the momentum and for the particle coordinate. Verification of the schemes was carried out on a problem that has an exact solution. It is shown that the symplectic five-stage RKN scheme provides a more accurate conservation of the total energy balance of the particle system than schemes of lower orders of accuracy. The stability studies of the schemes were performed using the Mathematica software package.

An implicit split-operator algorithm for the nonlinear time-dependent Schrödinger equation

The explicit split-operator algorithm is often used for solving the linear and nonlinear time-dependent Schrödinger equations. However, when applied to certain nonlinear time-dependent Schrödinger equations, this algorithm loses time reversibility and second-order accuracy, which makes it very inefficient. Here, we propose to overcome the limitations of the explicit split-operator algorithm by abandoning its explicit nature. We describe a family of high-order implicit split-operator algorithms that are norm-conserving, time-reversible, and very efficient. The geometric properties of the integrators are proven analytically and demonstrated numerically on the local control of a two-dimensional model of retinal. Although they are only applicable to separable Hamiltonians, the implicit split-operator algorithms are, in this setting, more efficient than the recently proposed integrators based on the implicit midpointmethod.

Fundamental derivation of two Boris solvers and the Ge-Marsden theorem.

It has been known for some time that when one uses the Lorentz force law, rather than Hamilton's equation, one can derive two basic algorithms for solving trajectories in a magnetic field formally similar to the velocity-Verlet (VV) and position-Verlet (PV) symplectic integrators independent of any finite-difference approximation. Because the Lorentz force law uses the mechanical rather than the canonical momentum, the resulting magnetic field algorithms are exact energy conserving, rather than symplectic. In general, both types of algorithms can only yield the exact trajectory in the limit of vanishing small time steps. This work shows that, for a constant magnetic field, both magnetic algorithms can be further modified so that their trajectories are exactly on the gyrocircle at finite time steps. The magnetic form of the PV integrator then becomes the well-known Boris solver, while the VV form yields a second, previously unknown Boris-type algorithm, unrelated to any finite-difference scheme. Remarkably, the modification needed for the trajectory to be exact is a reparametrization of the time step, reminiscent of the Ge-Marsden theorem.

Separability of the Planar 1/ρ2 Potential in Multiple Coordinate Systems

With a number of special Hamiltonians, solutions of the Schrödinger equation may be found by separation of variables in more than one coordinate system. The class of potentials involved includes a number of important examples, including the isotropic harmonic oscillator and the Coulomb potential. Multiply separable Hamiltonians exhibit a number of interesting features, including “accidental” degeneracies in their bound state spectra and often classical bound state orbits that always close. We examine another potential, for which the Schrödinger equation is separable in both cylindrical and parabolic coordinates: A z-independent V∝1/ρ2=1/(x2+y2) in three dimensions. All the persistent, bound classical orbits in this potential close, because all other orbits with negative energies fall to the center at ρ=0. When separated in parabolic coordinates, the Schrödinger equation splits into three individual equations, two of which are equivalent to the radial equation in a Coulomb potential—one equation with an attractive potential, the other with an equally strong repulsive potential.

Neural Canonical Transformation with Symplectic Flows

Canonical transformation plays a fundamental role in simplifying and solving classical Hamiltonian systems. We construct flexible and powerful canonical transformations as generative models using symplectic neural networks. The model transforms physical variables towards a latent representation with an independent harmonic oscillator Hamiltonian. Correspondingly, the phase space density of the physical system flows towards a factorized Gaussian distribution in the latent space. Since the canonical transformation preserves the Hamiltonian evolution, the model captures nonlinear collective modes in the learned latent representation. We present an efficient implementation of symplectic neural coordinate transformations and two ways to train the model. The variational free energy calculation is based on the analytical form of physical Hamiltonian. While the phase space density estimation only requires samples in the coordinate space for separable Hamiltonians. We demonstrate appealing features of neural canonical transformation using toy problems including two-dimensional ring potential and harmonic chain. Finally, we apply the approach to real-world problems such as identifying slow collective modes in alanine dipeptide and conceptual compression of the MNIST dataset.

Localisation and transport in bidimensional random models with separable Hamiltonians

We consider two bidimensional random models characterised by the following features: (a) their Hamiltonians are separable in polar coordinates and (b) the random part of the potential depends either on the angular coordinate or on the radial one, but not on both. The disorder correspondingly localises the angular or the radial part of the eigenfunctions. We analyse the analogies and the differences which exist between the selected 2D models and their 1D counterparts. We show how the analogies allow one to use correlated disorder to design a localisation length with pre-defined energy dependence and to produce directional localisation of the wavefunctions in models with angular disorder. We also discuss the importance of finite-size and resonance effects in shaping the eigenfunctions of the model with angular disorder; for the model with disorder associated to the radial variable we show under what conditions the localisation length coincides with the expression valid in the 1D case.

Efficient geometric integrators for nonadiabatic quantum dynamics. II. The diabatic representation.

Exact nonadiabatic quantum evolution preserves many geometric properties of the molecular Hilbert space. In the first paper of this series ["Paper I," S. Choi and J. Vaníček, J. Chem. Phys. 150, 204112 (2019)], we presented numerical integrators of arbitrary-order of accuracy that preserve these geometric properties exactly even in the adiabatic representation, in which the molecular Hamiltonian is not separable into kinetic and potential terms. Here, we focus on the separable Hamiltonian in diabatic representation, where the split-operator algorithm provides a popular alternative because it is explicit and easy to implement, while preserving most geometric invariants. Whereas the standard version has only second-order accuracy, we implemented, in an automated fashion, its recursive symmetric compositions, using the same schemes as in Paper I, and obtained integrators of arbitrary even order that still preserve the geometric properties exactly. Because the automatically generated splitting coefficients are redundant, we reduce the computational cost by pruning these coefficients and lower memory requirements by identifying unique coefficients. The order of convergence and preservation of geometric properties are justified analytically and confirmed numerically on a one-dimensional two-surface model of NaI and a three-dimensional three-surface model of pyrazine. As for efficiency, we find that to reach a convergence error of 10-10, a 600-fold speedup in the case of NaI and a 900-fold speedup in the case of pyrazine are obtained with the higher-order compositions instead of the second-order split-operator algorithm. The pyrazine results suggest that the efficiency gain survives in higher dimensions.

Efficient geometric integrators for nonadiabatic quantum dynamics. I. The adiabatic representation.

Geometric integrators of the Schrödinger equation conserve exactly many invariants of the exact solution. Among these integrators, the split-operator algorithm is explicit and easy to implement but, unfortunately, is restricted to systems whose Hamiltonian is separable into kinetic and potential terms. Here, we describe several implicit geometric integrators applicable to both separable and nonseparable Hamiltonians and, in particular, to the nonadiabatic molecular Hamiltonian in the adiabatic representation. These integrators combine the dynamic Fourier method with the recursive symmetric composition of the trapezoidal rule or implicit midpoint method, which results in an arbitrary order of accuracy in the time step. Moreover, these integrators are exactly unitary, symplectic, symmetric, time-reversible, and stable and, in contrast to the split-operator algorithm, conserve energy exactly, regardless of the accuracy of the solution. The order of convergence and conservation of geometric properties are proven analytically and demonstrated numerically on a two-surface NaI model in the adiabatic representation. Although each step of the higher order integrators is more costly, these algorithms become the most efficient ones if higher accuracy is desired; a thousand-fold speedup compared to the second-order trapezoidal rule (the Crank-Nicolson method) was observed for a wavefunction convergence error of 10-10. In a companion paper [J. Roulet, S. Choi, and J. Vaníček, J. Chem. Phys. 150, 204113 (2019)], we discuss analogous, arbitrary-order compositions of the split-operator algorithm and apply both types of geometric integrators to a higher-dimensional system in the diabatic representation.