Search

We present extensive new ab initio path integral Monte Carlo (PIMC) results for a variety of structural properties of warm dense hydrogen and beryllium. To deal with the fermion sign problem—an exponential computational bottleneck due to the antisymmetry of the electronic thermal density matrix—we employ the recently proposed [Y. Xiong and H. Xiong, J. Chem. Phys. 157, 094112 (2022); T. Dornheim et al., J. Chem. Phys. 159, 164113 (2023)] ξ-extrapolation method and find excellent agreement with the exact direct PIMC reference data where available. This opens up the intriguing possibility of studying a gamut of properties of light elements and potentially material mixtures over a substantial part of the warm dense matter regime, with direct relevance for astrophysics, material science, and inertial confinement fusion research. [ABSTRACT FROM AUTHOR]

A new multiple-time scale integration method is presented that propagates ab initio path integral molecular dynamics (PIMD). This method uses a large time step to generate an approximate geometrical configuration whose energy and gradient are evaluated at the level of an ab initio method, and then, a more precise integration scheme, e.g., the Bulirsch–Stoer method or velocity Verlet integration with a smaller time step, is used to integrate from the previous step using the computationally efficient interpolated potential energy surface constructed from two consecutive points. This method makes the integration of PIMD more efficient and accurate compared with the velocity Verlet integration. A Nos e ́ –Hoover chain thermostat combined with this new multiple-time scale method has good energy conservation even with a large time step, which is usually challenging in velocity Verlet integration for PIMD due to the very small chain mass when a large number of beads are used. The new method is used to calculate infrared spectra and free energy profiles to demonstrate its accuracy and capabilities. [ABSTRACT FROM AUTHOR]

DL_POLY Quantum 2.0, a vastly expanded software based on DL_POLY Classic 1.10, is a highly parallelized computational suite written in FORTRAN77 with a modular structure for incorporating nuclear quantum effects into large-scale/long-time molecular dynamics simulations. This is achieved by presenting users with a wide selection of state-of-the-art dynamics methods that utilize the isomorphism between a classical ring polymer and Feynman's path integral formalism of quantum mechanics. The flexible and user-friendly input/output handling system allows the control of methodology, integration schemes, and thermostatting. DL_POLY Quantum is equipped with a module specifically assigned for calculating correlation functions and printing out the values for sought-after quantities, such as dipole moments and center-of-mass velocities, with packaged tools for calculating infrared absorption spectra and diffusion coefficients. [ABSTRACT FROM AUTHOR]

Recent experiments by Brückner et al. [Science 380, 1357 (2023)] have observed an anomalous chain length dependence of the time of near approach of widely separated pairs of genomic elements on transcriptionally active chromosomal DNA. In this paper, I suggest that the anomaly may have its roots in internal friction between neighboring segments on the DNA backbone. The basis for this proposal is a model of chain dynamics formulated in terms of a continuum scaled Brownian walk (sBw) of polymerization index N. The sBw is an extension of the simple Brownian walk model widely used in path integral calculations of polymer properties, differing from it in containing an additional parameter H (the Hurst index) that can be tuned to produce varying degrees of correlation between adjacent monomers. A calculation using the sBw of the mean time τc for chain closure predicts—under the Wilemski–Fixman approximation for diffusion-controlled reactions—that at early times, τc varies as the 2/3 power of N, in close agreement with the findings of the Brückner et al. study. Other scaling relations of that study, including those related to the probability of loop formation and the mean square displacements of terminal monomers, are also satisfactorily accounted for by the model. [ABSTRACT FROM AUTHOR]

By using the recently derived universal discrete imaginary-time propagator of the harmonic oscillator, both thermodynamic and Hamiltonian energies can be given analytically and evaluated numerically at each imaginary time step for any short-time propagator. This work shows that, using only currently known short-time propagators, the Hamiltonian energy can be optimized to the twelfth-order, converging to the ground state energy of the harmonic oscillator in as few as three beads. This study makes it absolutely clear that the widely used second-order primitive approximation propagator, when used in computing thermodynamic energy, converges extremely slowly with an increasing number of beads. [ABSTRACT FROM AUTHOR]

Nuclear quantum effects play critical roles in a variety of molecular processes, especially in systems that contain hydrogen and other light nuclei, such as water. For water under ambient conditions, nuclear quantum effects are often interpreted as local effects resulting from a smearing of the hydrogen atom distribution. However, the orientational structure of water at interfaces determines long-range effects, such as electrostatics, through the O–H bond ordering that is impacted by nuclear quantum effects. In this work, I examine nuclear quantum effects on long-range electrostatics of water confined between hydrophobic walls using path integral simulations. To do so, I combine concepts from local molecular field theory with path integral methods at varying levels of approximation to develop efficient and physically intuitive approaches for describing long-range electrostatics in nonuniform quantum systems. Using these approaches, I show that quantum water requires larger electrostatic forces to achieve interfacial screening than the corresponding classical system. This work highlights the subtleties of electrostatics in nonuniform classical and quantum molecular systems, and the methods presented here are expected to be of use to efficiently model nuclear quantum effects in large systems. [ABSTRACT FROM AUTHOR]

Tensor networks have historically proven to be of great utility in providing compressed representations of wave functions that can be used for the calculation of eigenstates. Recently, it has been shown that a variety of these networks can be leveraged to make real time non-equilibrium simulations of dynamics involving the Feynman–Vernon influence functional more efficient. In this work, a tensor network is developed for non-perturbatively calculating the equilibrium correlation function for open quantum systems using the path integral methodology. These correlation functions are of fundamental importance in calculations of rates of reactions, simulations of response functions and susceptibilities, spectra of systems, etc. The influence of the solvent on the quantum system is incorporated through an influence functional, whose unconventional structure motivates the design of a new optimal matrix product-like operator that can be applied to the so-called path amplitude matrix product state. This complex-time tensor network path integral approach provides an exceptionally efficient representation of the path integral, enabling simulations for larger systems strongly interacting with baths and at lower temperatures out to longer time. The derivation, design, and implementation of this method are discussed along with a wide range of illustrations ranging from rate theory and symmetrized spin correlation functions to simulation of response of the Fenna–Matthews–Olson complex to light. [ABSTRACT FROM AUTHOR]

The ab initio path integral Monte Carlo (PIMC) method is one of the most successful methods in statistical physics, quantum chemistry and related fields, but its application to quantum degenerate Fermi systems is severely hampered by an exponential computational bottleneck: the notorious fermion sign problem. Very recently, Xiong and Xiong [J. Chem. Phys. 157, 094112 (2022)] have suggested to partially circumvent the sign problem by carrying out simulations of fictitious systems guided by an interpolating continuous variable ξ ∈ [−1, 1], with the physical Fermi- and Bose-statistics corresponding to ξ = −1 and ξ = 1. It has been proposed that information about the fermionic limit might be obtained by calculations within the bosonic sector ξ > 0 combined with an extrapolation throughout the fermionic sector ξ < 0, essentially bypassing the sign problem. Here, we show how the inclusion of the artificial parameter ξ can be interpreted as an effective penalty on the formation of permutation cycles in the PIMC simulation. We demonstrate that the proposed extrapolation method breaks down for moderate to high quantum degeneracy. Instead, the method constitutes a valuable tool for the description of large Fermi-systems of weak quantum degeneracy. This is demonstrated for electrons in a 2D harmonic trap and for the uniform electron gas (UEG), where we find excellent agreement (∼ 0.5 %) with exact configuration PIMC results in the high-density regime while attaining a speed-up exceeding 11 orders of magnitude. Finally, we extend the idea beyond the energy and analyze the radial density distribution (2D trap), as well as the static structure factor and imaginary-time density–density correlation function (UEG). [ABSTRACT FROM AUTHOR]

Bosonic exchange symmetry leads to fascinating quantum phenomena, from exciton condensation in quantum materials to the superfluidity of liquid 4He. Unfortunately, path integral molecular dynamics (PIMD) simulations of bosons are computationally prohibitive beyond ∼ 100 particles, due to a cubic scaling with the system size. We present an algorithm that reduces the complexity from cubic to quadratic, allowing the first simulations of thousands of bosons using PIMD. Our method is orders of magnitude faster, with a speedup that scales linearly with the number of particles and the number of imaginary time slices (beads). Simulations that would have otherwise taken decades can now be done in days. In practice, the new algorithm eliminates most of the added computational cost of including bosonic exchange effects, making them almost as accessible as PIMD simulations of distinguishable particles. [ABSTRACT FROM AUTHOR]

The direct integration of the harmonic oscillator path integral obscures the fundamental structure of its discrete, imaginary time propagator (density matrix). This work, by first proving an operator identity for contracting two free propagators into one in the presence of interaction, derives the discrete propagator by simple algebra without doing any integration. This discrete propagator is universal, having the same two hyperbolic coefficient functions for all short-time propagators. Individual short-time propagator only modifies the coefficient function's argument, its portal parameter, whose convergent order is the same as the thermodynamic energy. Moreover, the thermodynamic energy can be given in a closed form for any short-time propagator. Since the portal parameter can be systematically optimized by matching the expansion of the product of the two coefficients, any short-time propagator can be optimized sequentially, order by order, by matching the product coefficient's expansion alone, without computing the energy. Previous empirical findings on the convergence of fourth and sixth-order propagators can now be understood analytically. An eight-order convergent short-time propagator is also derived. [ABSTRACT FROM AUTHOR]

A positive Mu is a useful tool for investigating the spin density of radical species. The theoretical estimation of its behavior in a molecule requires the inclusion of a quantum effect due to the small mass of muonium. Herein, we performed ab initio a path integral molecular dynamics (PIMD) simulation, which accurately included a multi-dimensional quantum effect, for muoniated 9H-xanthene-9-thione (μXT). Our results showed that the quantum effect significantly increased the hyperfine coupling constant (HFCC) value of μXT, which qualitatively improved the calculated HFCC value, compared to the experimental one. In the PIMD simulation, the bond length between muonium and sulfur in μXT is longer than that between hydrogen and sulfur in a hydrogenated 9H-xanthene-9-thione (HXT), leading to a spin density transfer from XT (9H-xanthene-9-thione) to muonium due to neutral dissociations. Additionally, we found that the S–Mu bond in μXT prefers a structure perpendicular to the molecular plane, where the interaction between Mu and the singly occupied molecular orbital of μXT is the strongest. These structural changes resulted in a larger HFCC value in the PIMD simulation of μXT. [ABSTRACT FROM AUTHOR]

In silico property prediction based on density functional theory (DFT) is increasingly performed for crystalline materials. Whether quantitative agreement with experiment can be achieved with current methods is often an unresolved question, and may require detailed examination of physical effects such as electron correlation, reciprocal space sampling, phonon anharmonicity, and nuclear quantum effects (NQE), among others. In this work, we attempt first-principles equation of state prediction for the crystalline materials ScF3 and CaZrF6, which are known to exhibit negative thermal expansion (NTE) over a broad temperature range. We develop neural network (NN) potentials for both ScF3 and CaZrF6 trained to extensive DFT data, and conduct direct molecular dynamics prediction of the equation(s) of state over a broad temperature/pressure range. The NN potentials serve as surrogates of the DFT Hamiltonian with enhanced computational efficiency allowing for simulations with larger supercells and inclusion of NQE utilizing path integral approaches. The conclusion of the study is mixed: while some equation of state behavior is predicted in semiquantitative agreement with experiment, the pressure-induced softening phenomenon observed for ScF3 is not captured in our simulations. We show that NQE have a moderate effect on NTE at low temperature but does not significantly contribute to equation of state predictions at increasing temperature. Overall, while the NN potentials are valuable for property prediction of these NTE (and related) materials, we infer that a higher level of electron correlation, beyond the generalized gradient approximation density functional employed here, is necessary for achieving quantitative agreement with experiment. [ABSTRACT FROM AUTHOR]

The transport of excess protons and hydroxide ions in water underlies numerous important chemical and biological processes. Accurately simulating the associated transport mechanisms ideally requires utilizing ab initio molecular dynamics simulations to model the bond breaking and formation involved in proton transfer and path-integral simulations to model the nuclear quantum effects relevant to light hydrogen atoms. These requirements result in a prohibitive computational cost, especially at the time and length scales needed to converge proton transport properties. Here, we present machine-learned potentials (MLPs) that can model both excess protons and hydroxide ions at the generalized gradient approximation and hybrid density functional theory levels of accuracy and use them to perform multiple nanoseconds of both classical and path-integral proton defect simulations at a fraction of the cost of the corresponding ab initio simulations. We show that the MLPs are able to reproduce ab initio trends and converge properties such as the diffusion coefficients of both excess protons and hydroxide ions. We use our multi-nanosecond simulations, which allow us to monitor large numbers of proton transfer events, to analyze the role of hypercoordination in the transport mechanism of the hydroxide ion and provide further evidence for the asymmetry in diffusion between excess protons and hydroxide ions. [ABSTRACT FROM AUTHOR]

We develop a new simulation technique based on path-integral molecular dynamics for calculating ground-state tunneling splitting patterns from ratios of symmetrized partition functions. In particular, molecular systems are rigorously projected onto their J = 0 rotational state by an "Eckart spring" that connects two adjacent beads in a ring polymer. Using this procedure, the tunneling splitting can be obtained from thermodynamic integration at just one (sufficiently low) temperature. Converged results are formally identical to the values that would have been obtained by solving the full rovibrational Schrödinger equation on a given Born–Oppenheimer potential energy surface. The new approach is showcased with simulations of hydronium and methanol, which are in good agreement with wavefunction-based calculations and experimental measurements. The method will be of particular use for the study of low-barrier methyl rotations and other floppy modes, where instanton theory is not valid. [ABSTRACT FROM AUTHOR]

Based on a linearization approximation coupled with path integral formalism, we propose a method derived from the propagation of quasi-classical trajectories to simulate resonance Raman spectra. This method is based on ground state sampling followed by an ensemble of trajectories on the mean surface between the ground and excited states. The method was tested on three models and compared to a quantum mechanics solution based on a sum-over-states approach: harmonic and anharmonic oscillators and the HOCl molecule (hypochlorous acid). The method proposed is able to correctly characterize resonance Raman scattering and enhancement, including the description of overtones and combination bands. The absorption spectrum is obtained at the same time, and the vibrational fine structure can be reproduced for long excited state relaxation times. The method can also be applied to dissociating excited states (as is the case for HOCl). [ABSTRACT FROM AUTHOR]

This paper reports the release of PathSum, a new software suite of state-of-the-art path integral methods for studying the dynamics of single or extended systems coupled to harmonic environments. The package includes two modules, suitable for system–bath problems and extended systems comprising many coupled system–bath units, and is offered in C++ and Fortran implementations. The system–bath module offers the recently developed small matrix path integral (SMatPI) and the well-established iterative quasi-adiabatic propagator path integral (i-QuAPI) method for iteration of the reduced density matrix of the system. In the SMatPI module, the dynamics within the entanglement interval can be computed using QuAPI, the blip sum, time evolving matrix product operators, or the quantum–classical path integral method. These methods have distinct convergence characteristics and their combination allows a user to access a variety of regimes. The extended system module provides the user with two algorithms of the modular path integral method, applicable to quantum spin chains or excitonic molecular aggregates. An overview of the methods and code structure is provided, along with guidance on method selection and representative examples. [ABSTRACT FROM AUTHOR]

A simulation of the non-adiabatic dynamics of a quantum system coupled to dissipative environments poses significant challenges. New sophisticated methods are regularly being developed with an eye toward moving to larger systems and more complicated descriptions of solvents. Many of these methods, however, are quite difficult to implement and debug. Furthermore, trying to make the individual algorithms work together through a modular application programming interface can be quite difficult as well. We present a new, open-source software framework, QuantumDynamics.jl, designed to address these challenges. It provides implementations of a variety of perturbative and non-perturbative methods for simulating the dynamics of these systems. Most prominently, QuantumDynamics.jl supports hierarchical equations of motion and methods based on path integrals. An effort has been made to ensure maximum compatibility of the interface between the various methods. Additionally, QuantumDynamics.jl, being built on a high-level programming language, brings a host of modern features to explorations of systems, such as the usage of Jupyter notebooks and high level plotting, the possibility of leveraging high-performance machine learning libraries for further development. Thus, while the built-in methods can be used as end-points in themselves, the package provides an integrated platform for experimentation, exploration, and method development. [ABSTRACT FROM AUTHOR]

We use the modified Bigeleisen–Mayer equation to compute kinetic isotope effect values for non-enzymatic phosphoryl transfer reactions from classical and path integral molecular dynamics umbrella sampling. The modified form of the Bigeleisen–Mayer equation consists of a ratio of imaginary mode vibrational frequencies and a contribution arising from the isotopic substitution's effect on the activation free energy, which can be computed from path integral simulation. In the present study, we describe a practical method for estimating the frequency ratio correction directly from umbrella sampling in a manner that does not require normal mode analysis of many geometry optimized structures. Instead, the method relates the frequency ratio to the change in the mass weighted coordinate representation of the minimum free energy path at the transition state induced by isotopic substitution. The method is applied to the calculation of 16/18O and 32/34S primary kinetic isotope effect values for six non-enzymatic phosphoryl transfer reactions. We demonstrate that the results are consistent with the analysis of geometry optimized transition state ensembles using the traditional Bigeleisen–Mayer equation. The method thus presents a new practical tool to enable facile calculation of kinetic isotope effect values for complex chemical reactions in the condensed phase. [ABSTRACT FROM AUTHOR]

We study the linear energy response of the uniform electron gas to an external harmonic perturbation with a focus on resolving different contributions to the total energy. This has been achieved by carrying out highly accurate ab initio path integral Monte Carlo (PIMC) calculations for a variety of densities and temperatures. We report a number of physical insights into effects such as screening and the relative importance of kinetic and potential energies for different wave numbers. A particularly interesting finding is obtained from the observed non-monotonic behavior of the induced change in the interaction energy, which becomes negative for intermediate wave numbers. This effect is strongly dependent on the coupling strength and constitutes further direct evidence for the spatial alignment of electrons introduced in earlier works [T. Dornheim et al., Commun. Phys. 5, 304 (2022)]. The observed quadratic dependence on the perturbation amplitude in the limit of weak perturbations and the quartic dependence of perturbation amplitude corrections are consistent with linear and nonlinear versions of the density stiffness theorem. All PIMC simulation results are freely available online and can be used to benchmark new methods or as input for other calculations. [ABSTRACT FROM AUTHOR]

A large-scale quantum chemical calculation program, Dcdftbmd, was integrated with a Python-based advanced atomistic simulation program, i-PI. The implementation of a client–server model enabled hierarchical parallelization with respect to replicas and force evaluations. The established framework demonstrated that quantum path integral molecular dynamics simulations can be executed with high efficiency for systems consisting of a few tens of replicas and containing thousands of atoms. The application of the framework to bulk water systems, with and without an excess proton, demonstrated that nuclear quantum effects are significant for intra- and inter-molecular structural properties, including oxygen–hydrogen bond distance and radial distribution function around the hydrated excess proton. [ABSTRACT FROM AUTHOR]

A novel dielectric scheme is proposed for strongly coupled electron liquids, which handles quantum mechanical effects beyond the random phase approximation level and treats electronic correlations within the integral equation theory of classical liquids. The self-consistent scheme features a complicated dynamic local field correction functional and its formulation is guided by ab initio path integral Monte Carlo simulations. Remarkably, our scheme is capable of providing unprecedently accurate results for the static structure factor with the exception of the Wigner crystallization vicinity, despite the absence of adjustable or empirical parameters. [ABSTRACT FROM AUTHOR]

Fractional Brownian motion (fBm) is an experimentally-relevant, non-Markovian Gaussian stochastic process with long-ranged correlations between the increments, parametrised by the so-called Hurst exponent H ; depending on its value the process can be sub-diffusive (0 < H < 1 / 2) , diffusive (H = 1 / 2) or super-diffusive (1 / 2 < H < 1) . There exist three alternative equally often used definitions of fBm—due to Lévy and due to Mandelbrot and van Ness (MvN), which differ by the interval on which the time variable is formally defined. Respectively, the covariance functions of these fBms have different functional forms. Moreover, the MvN fBms have stationary increments, while for the Lévy fBm this is not the case. One may therefore be tempted to conclude that these are, in fact, different processes which only accidentally bear the same name. Recently determined explicit path integral representations also appear to have very different functional forms, which only reinforces the latter conclusion. Here we develop a unifying equivalent path integral representation of all three fBms in terms of Riemann–Liouville fractional integrals, which links the fBms and proves that they indeed belong to the same family. We show that the action in such a representation involves the fractional integral of the same form and order (dependent on whether H < 1 / 2 or H > 1 / 2 ) for all three cases, and differs only by the integration limits. [ABSTRACT FROM AUTHOR]

Two singularity theorems can be proven if one attempts to let a Lorentzian cobordism interpolate between two topologically distinct manifolds. On the other hand, Cartier and DeWitt-Morette have given a rigorous definition for quantum field theories (QFTs) by means of path integrals. This paper uses their results to study whether QFTs can be made compatible with topology changes. We show that path integrals over metrics need a finite norm for the latter and for degenerate metrics, this problem can sometimes be resolved with tetrads. We prove that already in the neighborhood of some cuspidal singularities, difficulties can arise to define certain QFTs. On the other hand, we show that simple QFTs can be defined around conical singularities that result from a topology change in a simple setup. We argue that the ground state of many theories of quantum gravity will imply a small cosmological constant and, during the expansion of the universe, will cause frequent topology changes. Unfortunately, it is difficult to describe the transition amplitudes consistently due to the aforementioned problems. We argue that one needs to describe QFTs by stochastic differential equations, and in the case of gravity, by Regge calculus in order to resolve this problem. [ABSTRACT FROM AUTHOR]

Speaker Diarization (SD) or speaker indexing is a procedure for automatically partitioning a conversation by the number of speakers into homogeneous segments. The trustworthy diarization method accurately estimates the variable length assertion, and it involves major steps such as speech detection, speaker merges, and speaker change. The major problem with the SD method is enhancing the readability of speech transcription. In this study, a hybrid method of feature extraction based on the Dynamic Mel Frequency Cepstral Coefficient (DMFCC) and Linear Prediction Coding (LPC) is proposed for SD. The Voice Activity Detection (VAD) method is utilized to detect the presence or absence of a speaker in the audio lecture, which is followed by speaker segmentation utilizing the extracted features. The Deep Convolutional Neural Network (DCNN) is utilized to determine the feature vector and cluster the speaker from the audio lecture. The results show that the proposed DMFCC-LPC delivers a robust performance on metrics such as accuracy, Diarization Error Rate (DER) and False Positive Rate (FPR) of 0.967, 0.31 and 0.119 on CALLHOME dataset, in contrast to the Speaker Siarization System using HXLP-DCNN with Sailfish Optimization Algorithm (SDS-HXLP-DCNN-SOA), Feature-Level fusion, and Self-supervised clustering with Path Integral Clustering (SSC-PIC). [ABSTRACT FROM AUTHOR]

T-stress is one of the necessary physical quantities to characterize the stress field at the crack tip, and the properties of J-integral under its action remain to be investigated. The expression of J-integral considering T-stress was derived in this paper. The numerical simulation method was used to verify the expression under mode I, mode II and mixed mode I+II loading conditions, and a calculation method of crack tip stress field parameters based on J-integral was given. The theoretical derivation proves that the path conservation of the J1-integral is not affected by T-stress, but the value of the J2-integral meets the linear relationship with the square root of the distance from the start and end point of the integral path to the crack tip, and the coefficient of J2-r curve is related to T-stress. The finite element simulation results show that the crack length of the specimen has a significant effect on the J-integral, while the mesh size has a small effect on the J-integral calculation results. Under the same loading condition, J-integral values of different sizes specimens are different, but the trend of J2-r curve change is consistent with the expression derived from theory. Under mode II and mixed mode I+II loading conditions, the solving accuracy of T-stress is high, while under mode I loading conditions, J2 ≈ 0, the solving accuracy is reduced due to factors such as rounding error. [ABSTRACT FROM AUTHOR]

The AdS/CFT correspondence states that certain conformal field theories are equivalent to string theories in a higher-dimensional anti-de Sitter space. One aspect of the correspondence is an equivalence of density matrices or, if one ignores normalizations, of positive operators. On the CFT side of the correspondence, any two positive operators A, B will satisfy the trace inequality Tr(AB) ≤ Tr(A)Tr(B). This relation holds on any Hilbert space H and is deeply associated with the fact that the algebra B(H ) of bounded operators on H is a type I von Neumann factor. Holographic bulk theories must thus satisfy a corresponding condition, which we investigate below. In particular, we argue that the Euclidean gravitational path integral respects this inequality at all orders in the semi-classical expansion and with arbitrary higher-derivative corrections. The argument relies on a conjectured property of the classical gravitational action, which in particular implies a positive action conjecture for quantum gravity wavefunctions. We prove this conjecture for Jackiw-Teitelboim gravity and we also motivate it for more general theories. [ABSTRACT FROM AUTHOR]

Supersymmetric elementary string states in the compactified heterotic string theory are described by small black holes that have zero area event horizon. In this paper we compute the supersymmetric index of such elementary string states using gravitational path integral. The dominant contribution to the path integral comes from an Euclidean rotating black hole solution of the supergravity theory with a finite area event horizon, but the logarithm of the index, computed from the saddle point, vanishes. Nevertheless we show that the solution is singular on certain subspaces of the horizon where higher derivative corrections can be important, and once the higher derivative corrections are taken into account the solution could yield a finite result for the logarithm of the index whose form agrees with the microscopic results up to an overall numerical constant. While the numerical constant is not determined in our analysis, we show that it is independent of the details of the compactification and even the number of non-compact dimensions, in agreement with the microscopic results. [ABSTRACT FROM AUTHOR]

The gravitational path integral can be used to compute the number of black hole states for a given energy window, or the free energy in a thermal ensemble. In this article we explain how to use the gravitational path integral to compute the separate number of bosonic and fermionic black hole microstates. We do this by comparing the partition function with and without the insertion of (−1)F. In particular we introduce a universal rotating black hole that contributes to the partition function in the presence of (−1)F. We study this problem for black holes in asymptotically flat space and in AdS, putting constraints on the high energy spectrum of holographic CFTs (not necessarily supersymmetric). Finally, we analyze wormhole contributions to related quantities. [ABSTRACT FROM AUTHOR]

We give a path integral construction of the quantum mechanical partition function for gauged finite groups. Our construction gives the quantization of a system of d, N × N matrices invariant under the adjoint action of the symmetric group SN. The approach is general to any discrete group. For a system of harmonic oscillators, i.e. for the non-interacting case, the partition function is given by the Molien-Weyl formula times the zero-point energy contribution. We further generalise the result to a system of non-square and complex matrices transforming under arbitrary representations of the gauge group. [ABSTRACT FROM AUTHOR]

The Euclidean path integral is compared to the thermal (canonical) partition function in curved static space-times. It is shown that if spatial sections are non-compact and there is no Killing horizon, the logarithms of these two quantities differ only by a term proportional to the inverse temperature, that arises from the vacuum energy. When spatial sections are bordered by Killing horizons the Euclidean path integral is not equal to the thermal partition function. It is shown that the expression for the Euclidean path integral depends on which integral is taken first: over coordinates or over momenta. In the first case the Euclidean path integral depends on the scattering phase shift of the mode and it is UV diverge. In the second case it is the total derivative and diverge on the horizon. Furthermore we demonstrate that there are three different definitions of the energy, and the derivative with respect to the inverse temperature of the Euclidean path integral does not give the value of any of these three types of energy. We also propose the new method of computation of the Euclidean path integral that gives the correct equality between the Euclidean path integral and thermal partition function for non-compact spaces with and without Killing horizon. [ABSTRACT FROM AUTHOR]

This paper considers a recently-proposed string theory on AdS3 × S3 × T4 with one unit of NS-NS flux (k = 1). We discuss interpretations of the target space, including connections to twistor geometry and a more conventional spacetime interpretation via the Wakimoto representation. We propose an alternative perspective on the role of the Wakimoto formalism in the k = 1 string, for which no large radius limit is required by the inclusion of extra operator insertions in the path integral. This provides an exact Wakimoto description of the worldsheet CFT. We also discuss an additional local worldsheet symmetry, Q(z), that emerges when k = 1 and show that this symmetry plays an important role in the localisation of the path integral to a sum over covering maps. We demonstrate the emergence of a rigid worldsheet translation symmetry in the radial direction of the AdS3, for which again the presence of Q(z) is crucial. We conjecture that this radial symmetry plays a key role in understanding, in the case of the k = 1 string, the encoding of the bulk physics on the two-dimensional boundary. [ABSTRACT FROM AUTHOR]

Defining quantum information quantities directly in bulk quantum gravity is a difficult problem due to the fluctuations of spacetime. Some progress was made recently in [1], which provided a bulk interpretation of the Bekenstein Hawking formula for two sided BTZ black holes in terms of the entanglement entropy of gravitational edge modes. We generalize those results to give a bulk entanglement entropy interpretation of the quantum extremal surface formula in AdS3 gravity, as applied to a single interval in the boundary theory. Our computation further supports the proposal that AdS3 gravity can be viewed as a topological phase in which the bulk gravity edge modes are anyons that transform under the quantum group . These edge modes appear when we cut open the Euclidean path integral along bulk co-dimension 2 slices, and satisfies a shrinkable boundary condition which ensures that the Gibbons-Hawking calculation gives the correct state counting. [ABSTRACT FROM AUTHOR]

We study the Hamiltonian structure of unimodular-like theories, where the cosmological constant (or other supposed constants of nature) are demoted from fixed parameters to classical constants of motion. No new local degrees of freedom are present as a result of a U(1) gauge invariance of the theory. Hamiltonian analysis of the action reveals that the only possible gauge fixing that can be enforced is setting the spatial components of the four-volume time vector T i ≈ 0 . As a consequence of this, the gauge-fixed unimodular path integral is equivalent to the minisuperspace unimodular path integral. However, should we break the U(1) gauge invariance, two things happen: a massless propagating degree of freedom appears, and the (gauge-invariant) zero-mode receives modified dynamics. The implications are investigated, with the phenomenology depending crucially on the target "constant". [ABSTRACT FROM AUTHOR]

We report a new permutationally invariant polynomial (PIP) fit to CCSD(T)/aug-cc-pVTZ energies for $ \hbox {CH}_5^{+} $ CH 5 + that provides fast analytical forces, unlike the original PIP fit of 2006. The new fit, which is slightly more precise than the previous one, is used in classical molecular dynamics, diffusion Monte Carlo and path integral molecular dynamics calculations of CH and HH radial distribution functions (RDFs) at temperatures of 10 and $ 50\,\hbox {K} $ 50 K . Corresponding RDFs are also reported for $ \hbox {CD}_{3}\hbox {H}_{2}^{+} $ CD 3 H 2 + . The well-known quantum localisation of the H atoms to the diatomic site from previous and present DMC calculations is maintained at $ 10\,\hbox {K} $ 10 K but shows additional delocalisation to the ' $ \hbox {CH}_{3}^{+} $ CH 3 + ' site at $ 50\,\hbox {K} $ 50 K . [ABSTRACT FROM AUTHOR]

An efficient path integral (PI) model for the accurate analysis of curved dielectric structures on coarse grids via the two-dimensional nonstandard finite-difference time-domain (NS-FDTD) technique is introduced in this paper. In contrast to previous PI implementations of the perfectly electric conductor case, which accommodates orthogonal cells in the vicinity of curved surfaces, the novel PI model employs the occupation ratio of dielectrics in the necessary cells, providing thus a straightforward and instructive means to treat an assortment of practical applications. For its verification, the reflection from a flat plate and the scattering from a cylinder using the PI model are investigated. Results indicate that the featured methodology can enable the reliable and precise modeling of arbitrarily shaped dielectrics in the NS-FDTD algorithm on coarse grids. [ABSTRACT FROM AUTHOR]

Random tensor networks are a powerful toy model for understanding the entanglement structure of holographic quantum gravity. However, unlike holographic quantum gravity, their entanglement spectra are flat. It has therefore been argued that a better model consists of random tensor networks with link states that are not maximally entangled, i.e., have non-trivial spectra. In this work, we initiate a systematic study of the entanglement properties of these networks. We employ tools from free probability, random matrix theory, and one-shot quantum information theory to study random tensor networks with bounded and unbounded variation in link spectra, and in cases where a subsystem has one or multiple minimal cuts. If the link states have bounded spectral variation, the limiting entanglement spectrum of a subsystem with two minimal cuts can be expressed as a free product of the entanglement spectra of each cut, along with a Marchenko–Pastur distribution. For a class of states with unbounded spectral variation, analogous to semiclassical states in quantum gravity, we relate the limiting entanglement spectrum of a subsystem with two minimal cuts to the distribution of the minimal entanglement across the two cuts. In doing so, we draw connections to previous work on split transfer protocols, entanglement negativity in random tensor networks, and Euclidean path integrals in quantum gravity. [ABSTRACT FROM AUTHOR]

Mutually beneficial cooperation is a common part of economic systems as firms in partial cooperation with others can often make a higher sustainable profit. Though cooperative games were popular in 1950s, recent interest in noncooperative games is prevalent despite the fact that cooperative bargaining seems to be more useful in economic and political applications. In this paper we assume that the strategy space and time are inseparable with respect to a contract. Furthermore, it is assumed that each firm's strategy polygon is a geodesic polygon which changes its shape every point of time with the stubbornness strategy surface of firm's executive board follow a Gaussian free field. This gives us more flexibility to deal with generalized geodesic cooperative games which is the main contribution of this paper. Under this environment we show that the strategy spacetime is a dynamic curved Liouville-like 2-brane quantum gravity surface under asymmetric information and that traditional Euclidean geometry fails to give a proper feedback Nash equilibrium. Cooperation occurs when two firms' strategies fall into each other's influence curvature in this strategy spacetime. Small firms in an economy dominated by large firms are subject to the influence of large firms. We determine an optimal feedback semicooperation of the small firm in this case using a Liouville-Feynman path integral method. [ABSTRACT FROM AUTHOR]

This paper considers a recently-proposed string theory on AdS3 × S3 × T4 with one unit of NS-NS flux (k = 1). We discuss interpretations of the target space, including connections to twistor geometry and a more conventional spacetime interpretation via the Wakimoto representation. We propose an alternative perspective on the role of the Wakimoto formalism in the k = 1 string, for which no large radius limit is required by the inclusion of extra operator insertions in the path integral. This provides an exact Wakimoto description of the worldsheet CFT. We also discuss an additional local worldsheet symmetry, Q(z), that emerges when k = 1 and show that this symmetry plays an important role in the localisation of the path integral to a sum over covering maps. We demonstrate the emergence of a rigid worldsheet translation symmetry in the radial direction of the AdS3, for which again the presence of Q(z) is crucial. We conjecture that this radial symmetry plays a key role in understanding, in the case of the k = 1 string, the encoding of the bulk physics on the two-dimensional boundary. [ABSTRACT FROM AUTHOR]

We report a new permutationally invariant polynomial (PIP) fit to CCSD(T)/aug-cc-pVTZ energies for $ \hbox {CH}_5^{+} $ CH 5 + that provides fast analytical forces, unlike the original PIP fit of 2006. The new fit, which is slightly more precise than the previous one, is used in classical molecular dynamics, diffusion Monte Carlo and path integral molecular dynamics calculations of CH and HH radial distribution functions (RDFs) at temperatures of 10 and $ 50\,\hbox {K} $ 50 K . Corresponding RDFs are also reported for $ \hbox {CD}_{3}\hbox {H}_{2}^{+} $ CD 3 H 2 + . The well-known quantum localisation of the H atoms to the diatomic site from previous and present DMC calculations is maintained at $ 10\,\hbox {K} $ 10 K but shows additional delocalisation to the ' $ \hbox {CH}_{3}^{+} $ CH 3 + ' site at $ 50\,\hbox {K} $ 50 K . [ABSTRACT FROM AUTHOR]

An exact representation of quantum mechanics using the language of phase-space variables provides a natural starting point to introduce and develop semiclassical approximations for the calculation of time correlation functions. Here, we introduce an exact path-integral formalism for calculations of multi-time quantum correlation functions as canonical averages over ring-polymer dynamics in imaginary time. The formulation provides a general formalism that exploits the symmetry of path integrals with respect to permutations in imaginary time, expressing correlations as products of imaginary-time-translation-invariant phase-space functions coupled through Poisson bracket operators. The method naturally recovers the classical limit of multi-time correlation functions and provides an interpretation of quantum dynamics in terms of "interfering trajectories" of the ring-polymer in phase space. The introduced phase-space formulation provides a rigorous framework for the future development of quantum dynamics methods that exploit the invariance of imaginary time path integrals to cyclic permutations. [ABSTRACT FROM AUTHOR]

The vibrational spectra of condensed and gas-phase systems are influenced by thequantum-mechanical behavior of light nuclei. Full-dimensional simulations of approximate quantum dynamics are possible thanks to the imaginary time path-integral (PI) formulation of quantum statistical mechanics, albeit at a high computational cost which increases sharply with decreasing temperature. By leveraging advances in machine-learned coarse-graining, we develop a PI method with the reduced computational cost of a classical simulation. We also propose a simple temperature elevation scheme to significantly attenuate the artifacts of standard PI approaches as well as eliminate the unfavorable temperature scaling of the computational cost. We illustrate the approach, by calculating vibrational spectra using standard models of water molecules and bulk water, demonstrating significant computational savings and dramatically improved accuracy compared to more expensive reference approaches. Our simple, efficient, and accurate method has prospects for routine calculations of vibrational spectra for a wide range of molecular systems - with an explicit treatment of the quantum nature of nuclei. [ABSTRACT FROM AUTHOR]

We present the equation of state of solid parahydrogen between 0.024 and 0.1 Å−3 at T = 4.2 K, calculated using path integral Monte Carlo simulations, with ab initio two-body and three-body interaction potentials. We correct for finite size simulation errors using potential tail corrections. Trotter factorization errors are accounted for either via extrapolation or by using a suitably small imaginary time step. We incorporate the three-body interaction using two methods: (1) the full inclusion method, where pair and three-body interactions are used in both Monte Carlo sampling and in the energy estimators, and (2) the perturbative method, where three-body interactions are omitted from sampling but are still present in energy estimations. Both treatments of the three-body interaction return very similar total energies and pressures. The presence of three-body interactions has only minor effects on the structural properties of the solid. Whereas the pair interaction, on its own, significantly overestimates the pressure of solid parahydrogen, the additional presence of the three-body interaction causes a severe underestimation of the pressure. Our findings suggest that accurate simulations of solid parahydrogen require four-body and possibly higher-order many-body interactions. It may also be the case that static interaction potentials are entirely unsuitable for simulations of solid parahydrogen at high densities. [ABSTRACT FROM AUTHOR]

We study the structural phase transition, originally associated with the highest superconducting critical temperature Tc measured in high-pressure sulfur hydride. A quantitative description of its pressure dependence has been elusive for any ab initio theory attempted so far, raising questions on the actual mechanism leading to the maximum of Tc. Here, we estimate the critical pressure of the hydrogen bond symmetrization in the Im 3 ¯ m structure, by combining density functional theory and quantum Monte Carlo simulations for electrons with path integral molecular dynamics for quantum nuclei. We find that the Tc maximum corresponds to pressures where local dipole moments dynamically form on the hydrogen sites, as precursors of the ferroelectric Im 3 ¯ m-R3m transition, happening at lower pressures. For comparison, we also apply the self-consistent harmonic approximation, whose ferroelectric critical pressure lies in between the ferroelectric transition estimated by path integral molecular dynamics and the local dipole formation. Nuclear quantum effects play a major role in a significant reduction (≈50 GPa) of the classical ferroelectric transition pressure at 200 K and in a large isotope shift (≈25 GPa) upon hydrogen-to-deuterium substitution of the local dipole formation pressure, in agreement with the corresponding change in the Tc maximum location. [ABSTRACT FROM AUTHOR]

We demonstrate the equivalence of two different conjectures in the literature for the holographic entanglement negativity in AdS3/CFT2, modulo certain constants. These proposals involve certain algebraic sums of bulk geodesics homologous to specific combinations of subsystems, and the entanglement wedge cross section (EWCS) backreacted by a cosmic brane for the conical defect geometry in the bulk gravitational path integral. It is observed that the former conjectures reproduce the field theory replica technique results in the large central charge limit whereas the latter involves constants related to the Markov gap. In this context, we establish an alternative construction for the EWCS of a single interval in a CFT2 at a finite temperature to resolve an issue for the latter proposal involving thermal entropy elimination for holographic entanglement negativity. Our construction for the EWCS correctly reproduces the corresponding field theory results modulo the Markov gap constant in the large central charge limit. [ABSTRACT FROM AUTHOR]

We applied the semiclassical initial value representation (SC-IVR) method with the classical electron analog to deal with electronically non-adiabatic reactive barriers and calculated the thermal reaction rate constant. The symmetric form of the flux–flux correlation function is used, and the matrix element of the Boltzmannized flux operator is derived using imaginary-time path integral techniques. This combined use of non-adiabatic SC-IVR and non-adiabatic path-integral sampling (NA-IVR&PI) is beyond the treatment of mean-field, and we analyze its performance in comparison with some existing mean-field methods for different scenarios of potential energy surface. We found a systematically better performance. One exception is the deep tunneling regime, where the mean-field ring-polymer instanton is superior. In the golden rule limit, where all these mean-field methods break down, the significant advantage of NA-IVR&PI is shown by using the electronic states for description of the dividing surface. [ABSTRACT FROM AUTHOR]

There are many processes in cell biology that can be modelled in terms of an actively switching particle. The continuous degrees of freedom of the particle evolve according to a hybrid stochastic differential equation whose drift term depends on a discrete internal or environmental state that switches according to a continuous time Markov chain. Examples include Brownian motion in a randomly switching environment, membrane voltage fluctuations in neurons, protein synthesis in gene networks, bacterial run-and-tumble motion, and motor-driven intracellular transport. In this paper we derive generalized Dean–Kawasaki (DK) equations for a population of actively switching particles, either independently switching or subject to a common randomly switching environment. In the case of a random environment, we show that the global particle density evolves according to a hybrid DK equation. Averaging with respect to the Gaussian noise processes in the absence of particle interactions yields a hybrid partial differential equation for the one-particle density. We use this to show how a randomly switching environment induces statistical correlations between the particles. We also discuss methods for handling the moment closure problem for interacting particles, including dynamical density functional theory and mean field theory. We then develop the analogous constructions for independently switching particles. In order to derive a DK equation, we introduce a discrete set of global densities that are indexed by the single-particle internal states, and take expectations with respect to the switching process. However, the resulting DK equation is no longer closed when particle interactions are included. We conclude by deriving Martin–Siggia–Rose–Janssen–de Dominicis path integrals for the global density equations in the absence of interactions, and relate this to recent field theoretic studies of Brownian gases and run-and-tumble particles. [ABSTRACT FROM AUTHOR]

In this paper, we construct a pointed CW complex called the magnitude homotopy type for a given metric space |$X$| and a real parameter |$\ell \geq 0$|⁠. This space is roughly consisting of all paths of length |$\ell $| and has the reduced homology group that is isomorphic to the magnitude homology group of |$X$|⁠. To construct the magnitude homotopy type, we consider the poset structure on the spacetime |$X\times \mathbb{R}$| defined by causal (time- or light-like) relations. The magnitude homotopy type is defined as the quotient of the order complex of an intervals on |$X\times \mathbb{R}$| by a certain subcomplex. The magnitude homotopy type gives a covariant functor from the category of metric spaces with |$1$| -Lipschitz maps to the category of pointed topological spaces. The magnitude homotopy type also has a "path integral" like expression for certain metric spaces. By applying discrete Morse theory to the magnitude homotopy type, we obtain a new proof of the Mayer–Vietoris-type theorem and several new results including the invariance of the magnitude under sycamore twist of finite metric spaces. [ABSTRACT FROM AUTHOR]

Observing the vertical diffusion distribution of methane fugitive emissions from oil/gas facilities is significant for predicting the pollutant's spatiotemporal transport and quantifying the random emission sources. A method is proposed for methane's vertical distribution mapping by combining the laser path-integral sensing in non-non-cooperative open paths and the computer-assisted tomography (CAT) techniques. It uses a vertical-plume-mapping optical path configuration and adapts the developed dynamic relaxation and simultaneous algebraic reconstruction technique (DR-SART) into methane-emission-distribution reconstruction. A self-made miniaturized TDLAS telemetry sensor provides a reliable path to integral concentration information in non-non-cooperative open paths, with Allan variance analysis yielding a 3.59 ppm·m sensitivity. We employed a six-indexes system for the reconstruction performance analysis of four potential optical path-projection configurations and conducted the corresponding validation experiment. The results have shown that that of multiple fan-beams combined with parallel-beam modes (MFPM) is better than the other optical path-projection configurations, and its reconstruction similarity coefficient (ε) is at least 22.4% higher. For the different methane gas bag-layout schemes, the reconstruction errors of maximum concentration (γm) are consistently around 0.05, with the positional errors of maximum concentration (δ) falling within the range of 0.01 to 0.025. Moreover, considering the trade-off between scanning duration and reconstruction accuracy, it is recommended to appropriately extend the sensor measurement time on a single optical path to mitigate the impact of mechanical vibrations induced by scanning motion. [ABSTRACT FROM AUTHOR]

On the basis of fractional calculus, we introduce an explicit formulation of the integral of controlled paths along Hölder rough paths in terms of Lebesgue integrals for fractional derivatives. The additivity with respect to the interval of integration, a fundamental property of the integral, is not apparent under the formulation because the fractional derivatives depend heavily on the endpoints of the interval of integration. In this paper, we provide a proof of the additivity of the integral under the formulation. Our proof seems to be simpler than those provided in previous studies and is suitable for utilizing the fractional calculus approach to rough path analysis. [ABSTRACT FROM AUTHOR]