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Accurate path integral Monte Carlo or molecular dynamics calculations of isotope effects have until recently been expensive because of the necessity to reduce three types of errors present in such calculations: statistical errors due to…

Chemical Physics · Physics 2017-05-10 Konstantin Karandashev , Jiri Vanicek

The shift in chemical equilibria due to isotope substitution is often exploited to gain insight into a wide variety of chemical and physical processes. It is a purely quantum mechanical effect, which can be computed exactly using…

Statistical Mechanics · Physics 2014-07-04 Michele Ceriotti , Thomas E. Markland

Fractionation of isotopes among distinct molecules or phases is a quantum effect which is often exploited to obtain insights on reaction mechanisms, biochemical, geochemical and atmospheric phenomena. Accurate evaluation of isotope ratios…

Chemical Physics · Physics 2015-06-23 Bingqing Cheng , Michele Ceriotti

The Feynman path integral approach for computing equilibrium isotope effects and isotope fractionation corrects the approximations made in standard methods, although at significantly increased computational cost. We describe an accelerated…

Quantum Physics · Physics 2017-05-10 Marcin Buchowiecki , Jiri Vanicek

Path integral implementation of the quantum instanton approximation currently belongs among the most accurate methods for computing quantum rate constants and kinetic isotope effects, but its use has been limited due to the rather high…

Chemical Physics · Physics 2017-05-10 Konstantin Karandashev , Jiri Vanicek

A general and rigorous methodology to compute the quantum equilibrium isotope effect is described. Unlike standard approaches, ours does not assume separability of rotational and vibrational motions and does not make the harmonic…

Chemical Physics · Physics 2015-05-13 Tomas Zimmermann , Jiri Vanicek

A general method for computing kinetic isotope effects is described. The method uses the quantum-instanton approximation and is based on the thermodynamic integration with respect to the mass of the isotopes and on the path-integral…

Chemical Physics · Physics 2007-05-23 Jiri Vanicek , William H. Miller

We introduce a new path integral Monte Carlo method for investigating nonadiabatic systems in thermal equilibrium and demonstrate an approach to reducing stochastic error. We derive a general path integral expression for the partition…

Chemical Physics · Physics 2019-07-11 Neil Raymond , Dmitri Iouchtchenko , Pierre-Nicholas Roy , Marcel Nooijen

A recently developed method, introduced in Phys. Rev. Lett. 94 (2005) 180403, Phys. Rev. B 72 (2005) 064302, Phys. Lett. A 344 (2005) 84, systematically improved the convergence of generic path integrals for transition amplitudes. This was…

Statistical Mechanics · Physics 2011-08-08 Jelena Grujic , Aleksandar Bogojevic , Antun Balaz

Path integrals are a central tool when it comes to describing quantum or thermal fluctuations of particles or fields. Their success dates back to Feynman who showed how to use them within the framework of quantum mechanics. Since then, path…

Statistical Mechanics · Physics 2022-08-31 Leticia F. Cugliandolo , Vivien Lecomte , Frédéric Van Wijland

This paper is concerned with high moment and pathwise error estimates for both velocity and pressure approximations of the Euler-Maruyama scheme for time discretization and its two fully discrete mixed finite element discretizations. The…

Numerical Analysis · Mathematics 2021-07-01 Liet Vo

This paper is concerned with high moment and pathwise error estimates for fully discrete mixed finite element approximattions of stochastic Navier-Stokes equations with general additive noise. The implicit Euler-Maruyama scheme and standard…

Numerical Analysis · Mathematics 2022-10-04 Xiaobing Feng , Liet Vo

Convergence of path integral simulations requires a substantial number of beads when quantum effects are significant. Traditional Trotter scaling approaches estimate the continuum limit through extrapolation, however they are restricted to…

Statistical Mechanics · Physics 2024-05-28 Sabry G Moustafa

We perform a thorough analysis on the choice of estimators for random series path integral methods. In particular, we show that both the thermodynamic (T-method) and the direct (H-method) energy estimators have finite variances and are…

Statistical Mechanics · Physics 2009-11-10 Cristian Predescu , Dubravko Sabo , J. D. Doll , David L. Freeman

This paper presents a new discretization error quantification method for the numerical integration of ordinary differential equations. The error is modelled by using the Wishart distribution, which enables us to capture the correlation…

Methodology · Statistics 2023-08-15 Naoki Marumo , Takeru Matsuda , Yuto Miyatake

Transported mediation effects may contribute to understanding how and why interventions may work differently when applied to new populations. However, we are not aware of any estimators for such effects. Thus, we propose several different…

Methodology · Statistics 2020-06-16 Kara E Rudolph , Jonathan Levy , Mark J van der Laan

Within path sampling framework, we show that probability distribution divergences, such as the Chernoff information, can be estimated via thermodynamic integration. The Boltzmann-Gibbs distribution pertaining to different Hamiltonians is…

Methodology · Statistics 2013-10-18 Silia Vitoratou , Ioannis Ntzoufras

We introduce a new methodology based on the multirevolution idea for constructing integrators for stochastic differential equations in the situation where the fast oscillations themselves are driven by a Stratonovich noise. Applications…

Numerical Analysis · Mathematics 2020-02-04 Adrien Laurent , Gilles Vilmart

The Inverse Problem for the estimation of a point-wise approximation error occurring at the discretization and solving of the system of partial differential equations is addressed. The set of the differences between the numerical solutions…

Numerical Analysis · Mathematics 2021-01-05 Aleksey Alekseev , Alexander Bondarev

Stochastic quantization in physics has been considered to provide a path integral representation of a probability distribution for Ito processes. It has been indicated that the stochastic quantization can involve a potential term, if the…

Systems and Control · Computer Science 2020-05-05 Masakazu Sano
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