Path Integral Monte Carlo Method Research Articles

Path integral Monte Carlo study of CO2 solvation in He4 clusters

We present a finite temperature quantum mechanical study of the dynamical and structural properties of small (4)He(N)-CO(2) clusters (N< or =17) using a path integral Monte Carlo (PIMC) method. The simulations were based on a He-CO(2) interaction potential with explicit dependence on the asymmetric stretch of the CO(2) molecule obtained at the CCSD(T) level. The shift of the CO(2) antisymmetric stretching (nu(3)) band origin and effective rotational constant were calculated as a function of the cluster size. In excellent agreement with experimental observations, the CO(2) vibrational band origin shifts and rotational constant show a turnaround near N=5, corresponding to a donut structure with the He atoms in equatorial positions of the linear dopant molecule.

Quantum-classical transition and decoherence in dissipative double-well potential systems: Monte Carlo algorithm

Localization transition and coherent-incoherent crossover in dissipative double-well potential systems are studied by the path-integral Monte Carlo method. By using an improved Monte Carlo algorithm developed by the authors, we determine a critical dissipation strength of localization transition for Ohmic damping by utilizing finite-size scaling analysis of the Kosterlitz--Thouless transition. We also determine a coherent-incoherent crossover by the disappearance of a peak in dynamical response functions. The obtained phase diagram indicates that both localization and coherent-incoherent crossover occur even for the small-barrier limit, where the system cannot be truncated to a two-state model.

Numerical study of transport through a single impurity in a spinful Tomonaga–Luttinger liquid

The single impurity problem in a spinful Tomonaga--Luttinger liquid is studied numerically using path-integral Monte Carlo methods. The advantage of our approach is that the system allows for extensive analyses of charge and spin conductance in the nonperturbative regime. By closely examining the behavior of conductances at low temperatures, in the presence of a finite backward scattering barrier due to the impurity, we identified four distinct phases characterized by either perfect transmission or reflection of charge and spin channels. Our phase diagram for an intermediate scattering strength is consistent with the standard perturbative renormalization group (RG) analysis in the limit of weak and strong backward scatterings, in the sense that all our phase boundaries interpolate the two limiting cases. Further investigations show, however, that precise location and form of our phase boundaries are not trivially explained by the standard RG analysis, e.g., some part of the phase diagram looks much similar to the weak backscattering limit, whereas some other part is clearly derived from the opposite limit. In order to give a more intuitive interpretation of such behaviors, we also reconsidered our impurity problem from the viewpoint of a quantum Brownian motion picture.

Properties of Bose-Einstein condensates in a quasi-one-dimensional box trap

We present numerical studies of Bose-Einstein condensates in an optical box trap. The box trap is modeled by using Gaussian-wall or hard-wall trapping potentials along the boundary of the box to mimic a recent experimental setup. In order to study a quasi-one-dimensional system, the Gaussian walls are separated differently along the axial and radial directions. Furthermore, the two-body interaction is described by a hard-sphere potential, whose radius equals the $s$-wave scattering length. Using a finite-temperature path integral Monte Carlo method, we have calculated the density profiles of the system as a function of the temperature, the strength of the two-body interaction, and the number of particles. Our numerical results show clearly the Tonks-gas--like behavior in the strong interaction limit. In addition, we have compared our numerical data with the experimental data and theoretical results, and found that our simulation data agree with them quantitatively.

Mathematical aspects of quantum annealing

Sufficient conditions for convergence of quantum annealing are derived for optimization problems represented by the Ising model. Three different types of time evolution are considered; the real-time Schrödinger equation, the path-integral Monte Carlo method and the Green's function Monte Carlo method. It is proved that the system under each dynamics reaches the target solution in the limit of infinite time if the transverse field, representing the strength of quantum fluctuations, decreases inversely proportionally to the power of time in the asymptotic region.

Finite-temperature properties of binary mixtures of two Bose-Einstein condensates

This work reports studies of a mixture of two interacting Bose condensates in a quasi-one-dimensional geometry using a finite-temperature path-integral Monte Carlo method. For weakly interacting dilute gases, the interactions between atoms are modeled by a hard-sphere potential whose core radius equals its corresponding scattering length. The effect of both the temperature and the interspecies interaction on the static properties, such as the density profile and the superfluid fraction, is discussed. Our results show that for repulsive intra- and interspecies interactions, the presence of the interspecies interactions dramatically changes the structure of both the density profile and the superfluid fraction, and two species are seen to partially separate in space, and there is a finite-size effect on the phase separation between two partially separating Bose-Einstein condensates. In general, our results agree with the theoretical predictions and experimental observations.

Pairing and superfluid properties of dilute fermion gases at unitarity

We study the system of a dilute gas of fermions in three dimensions, with attractive interactions tuned to the unitarity point, using the nonperturbative restricted path-integral Monte Carlo method. The pairing and superfluid properties of this system are calculated at finite temperature. The total energy at very low temperature from our results agrees closely with that of previous ground-state quantum Monte Carlo calculations. We identify the temperature ${T}^{*}\ensuremath{\approx}0.70{ϵ}_{F}$, below which pairing correlations develop, and estimate the critical temperature for the superfluid transition ${T}_{c}\ensuremath{\approx}0.245{ϵ}_{F}$ from a finite size scaling analysis of the superfluid density.

Crystallization in Mass‐Asymmetric Electron‐Hole Bilayers

AbstractWe consider a mass‐asymmetric electron and hole bilayer. Electron and hole Coulomb correlations and electron and hole quantum effects are treated on first principles by path integral Monte Carlo methods. For a fixed layer separation we vary the mass ratio M of holes and electrons between 1 and 100 and analyze the structural changes in the system. While, for the chosen density, the electrons are in a nearly homogeneous state, the hole arrangement changes from homogeneous to localized, with increasing M, which is verified for both, mesoscopic bilayers in a parabolic trap and for a macroscopic system. (© 2007 WILEY‐VCH Verlag GmbH &amp; Co. KGaA, Weinheim)

Path Integral Hybrid Monte Carlo Study on Structure of Small Helium-4 Clusters Doped with a Linear Molecule

Microscopic structure of small helium-4 clusters doped with a carbonyl sulfide molecule, OCS(4He)N, at 0.37 K is studied by the path integral hybrid Monte Carlo method; the size of the cluster N ranges from N=2 to N=5. In all the cases examined in the present study, the helium atoms are localized around the carbon atom of the OCS molecule, forming a doughnut-type structure around the molecular axis. Bosonic exchange among the helium atoms is found to be promoted in the doughnut region, showing an anisotropic “superfluid” response of the clusters.

USING DISCRETE VARIABLE REPRESENTATION PATH INTEGRAL MONTE CARLO WITH METROPOLIS SAMPLING TO COMPUTE GROUND STATE WAVEFUNCTIONS

The discrete variable representation (DVR) matrix dynamics formulation of the path integral Monte Carlo (PIMC) method, implemented numerically in a way that enables Metropolis sampling to be employed, is proposed as a means of computing ground state quantum wavefunctions. A key advantage of the DVR-PIMC approach is that customized marginal potentials may be employed, leading to significantly larger PIMC time step sizes, and substantial reductions in computational (CPU) effort. An additional key advantage of the present implementation is that the DVR provides a natural set of interpolant functions that can be used for accurate interpolation and extrapolation of function and tensor quantities away from predefined grid points. The new method is applied here to compute the ground state wavefunction of a model one degree-of-freedom (1 DOF) Morse oscillator system. A one-to-two order-of-magnitude reduction in CPU effort is observed, in comparison with a conventional PIMC simulation. The generalization for many DOFs is straightforward, and expected to result in even greater performance enhancement.

Monte Carlo approach to the decay rate of a metastable system with an arbitrarily shaped barrier

A path integral Monte Carlo method based on the fast-Fourier transform technique combined with the important sampling method is proposed to calculate the decay rate of a metastable quantum system with an arbitrary shape of a potential barrier. The contribution of all fluctuation actions is included which can be used to check the accuracy of the usual steepest-descent approximation, namely, the perturbation expansion of potential. The analytical approximation is found to produce the decay rate of a particle in a cubic potential being about 20% larger than the Monte Carlo data at the crossover temperature. This disagreement increases with increasing complexity of the potential shape. We also demonstrate via Langevin simulation that the postsaddle potential influences strongly upon the classical escape rate.

Rotational fluctuation of molecules in quantum clusters. I. Path integral hybrid Monte Carlo algorithm

In this paper, we present a path integral hybrid Monte Carlo (PIHMC) method for rotating molecules in quantum fluids. This is an extension of our PIHMC for correlated Bose fluids [S. Miura and J. Tanaka, J. Chem. Phys. 120, 2160 (2004)] to handle the molecular rotation quantum mechanically. A novel technique referred to be an effective potential of quantum rotation is introduced to incorporate the rotational degree of freedom in the path integral molecular dynamics or hybrid Monte Carlo algorithm. For a permutation move to satisfy Bose statistics, we devise a multilevel Metropolis method combined with a configurational-bias technique for efficiently sampling the permutation and the associated atomic coordinates. Then, we have applied the PIHMC to a helium-4 cluster doped with a carbonyl sulfide molecule. The effects of the quantum rotation on the solvation structure and energetics were examined. Translational and rotational fluctuations of the dopant in the superfluid cluster were also analyzed.

Torsional anharmonicity in the conformational analysis of tryptamine

In this paper we calculate the relative conformer populations of the tryptamine molecule. Our approach combines high level electronic structure conformer energies with harmonic frequencies and an anharmonic treatment of the torsional motions using the torsional path integral Monte Carlo method. We have developed a 3-D potential energy surface as a function of the torsional coordinates at the B3LYP/6-31+G(d) level using 2535 grid points. Eight conformers of tryptamine were found to be significantly populated at 430 K as opposed to the experimental observation of seven. This, along with further comparisons with various experimental data, leads us to suppose that conformer interconversion occurs during the cooling phases of many of the experiments. The ordering of the calculated populations fits well with available experimental data. Torsional anharmonicity is found to affect conformer populations more significantly at 430 K than at 100 K (although overall the effects are small), while quantum mechanical effects are not important at either temperature.

Torsional anharmonicity in transition state theory calculations

We present a new application for the Torsional Path Integral Monte Carlo (TPIMC) method in which the TPI partition functions are introduced into the calculation of Transition State Theory (TST) rate constants. In this way, an explicit treatment of torsional anharmonicity is included in the TST calculations and the magnitude of these effects can be assessed. The new method is tested on the C(2)H(6) + H hydrogen abstraction reaction and concerted hydrogen transfer in the carbonic acid dimer, for which we have developed torsional potential energy surfaces. For the C(2)H(6) + H reaction the rate constants are halved at room temperature on including a treatment of torsional anharmonicity, while the effects are found to be much smaller for the hydrogen transfer reaction in the carbonic acid dimer.

Path integral Monte Carlo calculations of dense hydrogen and helium thermodynamics

This paper is devoted to first-principles calculations of hydrogen and helium thermodynamics. We use the direct path integral Monte Carlo method to compute isochors and isotherms in a wide range of parameters in comparison with available theoretical and experimental results. New results for hydrogen and hydrogen–helium plasmas with the mass concentration of helium are analysed with the help of a model based on the chemical picture.

Hybrid quantum/classical path integral approach for simulation of hydrogen transfer reactions in enzymes

A hybrid quantum/classical path integral Monte Carlo (QC-PIMC) method for calculating the quantum free energy barrier for hydrogen transfer reactions in condensed phases is presented. In this approach, the classical potential of mean force along a collective reaction coordinate is calculated using umbrella sampling techniques in conjunction with molecular dynamics trajectories propagated according to a mapping potential. The quantum contribution is determined for each configuration along the classical trajectory with path integral Monte Carlo calculations in which the beads move according to an effective mapping potential. This type of path integral calculation does not utilize the centroid constraint and can lead to more efficient sampling of the relevant region of conformational space than free-particle path integral sampling. The QC-PIMC method is computationally practical for large systems because the path integral sampling for the quantum nuclei is performed separately from the classical molecular dynamics sampling of the entire system. The utility of the QC-PIMC method is illustrated by an application to hydride transfer in the enzyme dihydrofolate reductase. A comparison of this method to the quantized classical path and grid-based methods for this system is presented.

Equation of state of an interacting Bose gas at finite temperature: A path-integral Monte Carlo study

By using exact path-integral Monte Carlo methods we calculate the equation of state of an interacting Bose gas as a function of temperature both below and above the superfluid transition. The universal character of the equation of state for dilute systems and low temperatures is investigated by modeling the interatomic interactions using different repulsive potentials corresponding to the same $s$-wave scattering length. The results obtained for the energy and the pressure are compared to the virial expansion for temperatures larger than the critical temperature. At very low temperatures we find agreement with the ground-state energy calculated using the diffusion Monte Carlo method.

Quantum-Classical Transition in Dissipative Double-Well Systems – A Numerical Study by a New Monte Carlo Scheme –

Thermodynamics of dissipative quantum systems with double-well potentials is studied by the path-integral Monte Carlo (PIMC) method without truncation to the two-state model. For efficient simulation at low temperatures, we develop a new scheme of local update based on approximate decomposition of the Boltzmann weight to the Gaussian distributions. Localization transition induced by ohmic dissipation is clarified numerically for arbitrary potential barriers.

Quantum mechanical single molecule partition function from path integral Monte Carlo simulations

An algorithm for calculating the partition function of a molecule with the path integral Monte Carlo method is presented. Staged thermodynamic perturbation with respect to a reference harmonic potential is utilized to evaluate the ratio of partition functions. Parallel tempering and a new Monte Carlo estimator for the ratio of partition functions are implemented here to achieve well converged simulations that give an accuracy of 0.04 kcal/mol in the reported free energies. The method is applied to various test systems, including a catalytic system composed of 18 atoms. Absolute free energies calculated by this method lead to corrections as large as 2.6 kcal/mol at 300 K for some of the examples presented.

Spatial Delocalization in para-H2 Clusters

We applied the quantum path integral Monte Carlo method for the study of (para-H)N (N = 5-33) clusters at T = 2 K, exploring static and dynamic order, which originates from the effects of zero-point energy, kinetic energy, and thermal fluctuations in quantum clusters. Information on dynamic structure was inferred from the asymptotic tails of the cage correlation function calculated from the centroid Monte Carlo trajectory. The centroid cage correlation function decays to zero for large clusters (N = 15-33), manifesting the interchange of molecules between different solvation shells, with statistically diminishing back interchange. Further evidence for the floppiness of para-hydrogen clusters emerges from the Monte Carlo evolution of the centroid of a tagged molecule, which exhibits significant changes in the list of its first and second solvation shells due to the interchange of molecules between these shells.