Reconstruction of thermally-symmetrized quantum autocorrelation functions from imaginary-time data

In this paper, I propose a technique for recovering quantum dynamical information from imaginary-time data via the resolution of a one-dimensional Hamburger moment problem. It is shown that the quantum autocorrelation functions are uniquely determined by and can be reconstructed from their sequence of derivatives at origin. A general class of reconstruction algorithms is then identified, according to Theorem 3. The technique is advocated as especially effective for a certain class of quantum problems in continuum space, for which only a few moments are necessary. For such problems, it is argued that the derivatives at origin can be evaluated by Monte Carlo simulations via estimators of finite variances in the limit of an infinite number of path variables. Finally, a maximum entropy inversion algorithm for the Hamburger moment problem is utilized to compute the quantum rate of reaction for a one-dimensional symmetric Eckart barrier.Comment: 15 pages, no figures, to appear in Phys. Rev.

Thermodynamics and equilibrium structure of Ne_38 cluster: Quantum Mechanics versus Classical

The equilibrium properties of classical LJ_38 versus quantum Ne_38 Lennard-Jones clusters are investigated. The quantum simulations use both the Path-Integral Monte-Carlo (PIMC) and the recently developed Variational-Gaussian-Wavepacket Monte-Carlo (VGW-MC) methods. The PIMC and the classical MC simulations are implemented in the parallel tempering framework. The VGW method is used to locate and characterize the low energy states of Ne_38, which are then further refined by PIMC calculations. Unlike the classical case, the ground state of Ne_38 is a liquid-like structure. Among the several liquid-like states with energies below the two symmetric states (O_h and C_5v), the lowest two exhibit strong delocalization over basins associated with at least two classical local minima. Because the symmetric structures do not play an essential role in the thermodynamics of Ne_38, the quantum heat capacity is a featureless curve indicative of the absence of any structural transformations. Good agreement between the two methods, VGW and PIMC, is obtained.Comment: 13 pages, 9 figure

Entropic effects in large-scale Monte Carlo simulations

The efficiency of Monte Carlo samplers is dictated not only by energetic effects, such as large barriers, but also by entropic effects that are due to the sheer volume that is sampled. The latter effects appear in the form of an entropic mismatch or divergence between the direct and reverse trial moves. We provide lower and upper bounds for the average acceptance probability in terms of the Renyi divergence of order 1/2. We show that the asymptotic finitude of the entropic divergence is the necessary and sufficient condition for non-vanishing acceptance probabilities in the limit of large dimensions. Furthermore, we demonstrate that the upper bound is reasonably tight by showing that the exponent is asymptotically exact for systems made up of a large number of independent and identically distributed subsystems. For the last statement, we provide an alternative proof that relies on the reformulation of the acceptance probability as a large deviation problem. The reformulation also leads to a class of low-variance estimators for strongly asymmetric distributions. We show that the entropy divergence causes a decay in the average displacements with the number of dimensions n that are simultaneously updated. For systems that have a well-defined thermodynamic limit, the decay is demonstrated to be n^{-1/2} for random-walk Monte Carlo and n^{-1/6} for Smart Monte Carlo (SMC). Numerical simulations of the LJ_38 cluster show that SMC is virtually as efficient as the Markov chain implementation of the Gibbs sampler, which is normally utilized for Lennard-Jones clusters. An application of the entropic inequalities to the parallel tempering method demonstrates that the number of replicas increases as the square root of the heat capacity of the system.Comment: minor corrections; the best compromise for the value of the epsilon parameter in Eq. A9 is now shown to be log(2); 13 pages, 4 figures, to appear in PR

Extrapolated High-Order Propagators for Path Integral Monte Carlo Simulations

We present a new class of high-order imaginary time propagators for path-integral Monte Carlo simulations by subtracting lower order propagators. By requiring all terms of the extrapolated propagator be sampled uniformly, the subtraction only affects the potential part of the path integral. The negligible violation of positivity of the resulting path integral at small time steps has no discernable affect on the accuracy of our method. Thus in principle arbitrarily high order algorithms can be devised for path-integral Monte Carlo simulations. We verify this claim is by showing that fourth, sixth, and eighth order convergence can indeed be achieved in solving for the ground state of strongly interacting quantum many-body systems such as bulk liquid $^4$He.Comment: 9 pages and 3 figures. Submitted to J. Chem. Phy

Phase changes in selected Lennard-Jones X_{13-n}Y_n clusters

Detailed studies of the thermodynamic properties of selected binary Lennard-Jones clusters of the type X_{13-n}Y_n (where n=1,2,3) are presented. The total energy, heat capacity and first derivative of the heat capacity as a function of temperature are calculated by using the classical and path integral Monte Carlo methods combined with the parallel tempering technique. A modification in the phase change phenomena from the presence of impurity atoms and quantum effects is investigated.Comment: 14 pages, 13 figures. submitted to J. Chem. Phy

Upon the existence of short-time approximations of any polynomial order for the computation of density matrices by path integral methods

In this article, I provide significant mathematical evidence in support of the existence of short-time approximations of any polynomial order for the computation of density matrices of physical systems described by arbitrarily smooth and bounded from below potentials. While for Theorem 2, which is ``experimental'', I only provide a ``physicist's'' proof, I believe the present development is mathematically sound. As a verification, I explicitly construct two short-time approximations to the density matrix having convergence orders 3 and 4, respectively. Furthermore, in the Appendix, I derive the convergence constant for the trapezoidal Trotter path integral technique. The convergence orders and constants are then verified by numerical simulations. While the two short-time approximations constructed are of sure interest to physicists and chemists involved in Monte Carlo path integral simulations, the present article is also aimed at the mathematical community, who might find the results interesting and worth exploring. I conclude the paper by discussing the implications of the present findings with respect to the solvability of the dynamical sign problem appearing in real-time Feynman path integral simulations.Comment: 19 pages, 4 figures; the discrete short-time approximations are now treated as independent from their continuous version; new examples of discrete short-time approximations of order three and four are given; a new appendix containing a short review on Brownian motion has been added; also, some additional explanations are provided here and there; this is the last version; to appear in Phys. Rev.

Local Variational Principle

A generalization of the Gibbs-Bogoliubov-Feynman inequality for spinless particles is proven and then illustrated for the simple model of a symmetric double-well quartic potential. The method gives a pointwise lower bound for the finite-temperature density matrix and it can be systematically improved by the Trotter composition rule. It is also shown to produce groundstate energies better than the ones given by the Rayleigh-Ritz principle as applied to the groundstate eigenfunctions of the reference potentials. Based on this observation, it is argued that the Local Variational Principle performs better than the equivalent methods based on the centroid path idea and on the Gibbs-Bogoliubov-Feynman variational principle, especially in the range of low temperatures.Comment: 15 pages, 5 figures, one more section adde

Feedback-optimized parallel tempering Monte Carlo

We introduce an algorithm to systematically improve the efficiency of parallel tempering Monte Carlo simulations by optimizing the simulated temperature set. Our approach is closely related to a recently introduced adaptive algorithm that optimizes the simulated statistical ensemble in generalized broad-histogram Monte Carlo simulations. Conventionally, a temperature set is chosen in such a way that the acceptance rates for replica swaps between adjacent temperatures are independent of the temperature and large enough to ensure frequent swaps. In this paper, we show that by choosing the temperatures with a modified version of the optimized ensemble feedback method we can minimize the round-trip times between the lowest and highest temperatures which effectively increases the efficiency of the parallel tempering algorithm. In particular, the density of temperatures in the optimized temperature set increases at the "bottlenecks'' of the simulation, such as phase transitions. In turn, the acceptance rates are now temperature dependent in the optimized temperature ensemble. We illustrate the feedback-optimized parallel tempering algorithm by studying the two-dimensional Ising ferromagnet and the two-dimensional fully-frustrated Ising model, and briefly discuss possible feedback schemes for systems that require configurational averages, such as spin glasses.Comment: 12 pages, 14 figure

Impaired Caveolae Function and Upregulation of Alternative Endocytic Pathways Induced by Experimental Modulation of Intersectin-1s Expression in Mouse Lung Endothelium

Intersectin-1s (ITSN-1s), a protein containing five SH3 (A-E) domains, regulates via the SH3A the function of dynamin-2 (dyn2) at the endocytic site. ITSN-1s expression was modulated in mouse lung endothelium by liposome delivery of either a plasmid cDNA encoding myc-SH3A or a specific siRNA targeting ITSN-1 gene. The lung vasculature of SH3A-transduced and ITSN-1s- deficient mice was perfused with gold albumin (Au-BSA) to analyze by electron microscopy the morphological intermediates and pathways involved in transendothelial transport or with dinitrophenylated (DNP)-BSA to quantify by ELISA its transport. Acute modulation of ITSN-1s expression decreased the number of caveolae, impaired their transport, and opened the interendothelial junctions, while upregulating compensatory nonconventional endocytic/transcytotic structures. Chronic inhibition of ITSN-1s further increased the occurrence of nonconventional intermediates and partially restored the junctional integrity. These findings indicate that ITSN-1s expression is required for caveolae function and efficient transendothelial transport. Moreover, our results demonstrate that ECs are highly adapted to perform their transport function while maintaining lung homeostasis

Analysis of path integrals at low temperature : Box formula, occupation time and ergodic approximation

We study the low temperature behaviour of path integrals for a simple one-dimensional model. Starting from the Feynman-Kac formula, we derive a new functional representation of the density matrix at finite temperature, in terms of the occupation times of Brownian motions constrained to stay within boxes with finite sizes. From that representation, we infer a kind of ergodic approximation, which only involves double ordinary integrals. As shown by its applications to different confining potentials, the ergodic approximation turns out to be quite efficient, especially in the low-temperature regime where other usual approximations fail