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Recent work shows that strong stability and dimensionality freedom are essential for robust numerical integration of thermostatted ring-polymer molecular dynamics (T-RPMD) and path-integral molecular dynamics (PIMD), without which standard…

Chemical Physics · Physics 2021-01-11 Jorge L. Rosa-Raíces , Jiace Sun , Nawaf Bou-Rabee , Thomas F. Miller

We introduce mapping-variable ring polymer molecular dynamics (MV-RPMD), a model dynamics for the direct simulation of multi-electron processes. An extension of the RPMD idea, this method is based on an exact, imaginary time path-integral…

Statistical Mechanics · Physics 2015-06-17 Nandini Ananth

We introduce the coherent state mapping ring-polymer molecular dynamics (CS-RPMD), a new method that accurately describes electronic non-adiabatic dynamics with explicit nuclear quantization. This new approach is derived by using coherent…

Chemical Physics · Physics 2018-01-17 Sutirtha Chowdhury , Pengfei Huo

Path-integral-based molecular dynamics (MD) simulations are widely used for the calculation of numerically exact quantum Boltzmann properties and approximate dynamical quantities. A nearly universal feature of MD numerical integration…

Chemical Physics · Physics 2019-09-25 Roman Korol , Nawaf Bou-Rabee , Thomas F. Miller

A path-integral hybrid Monte Carlo approach with enveloping bridging potentials (PIHMC-EBP) is proposed for calculating numerically exact tunneling splittings in molecular systems. The central idea is to construct an approximately…

Chemical Physics · Physics 2026-04-15 Yu-Chen Wang , Jeremy O. Richardson

We extend ring-polymer molecular dynamics (RPMD) to allow for the direct simulation of general, electronically non-adiabatic chemical processes. The kinetically constrained (KC) RPMD method uses the imaginary-time path-integral…

Statistical Mechanics · Physics 2014-03-05 Artur R. Menzeleev , Franziska Bell , Thomas F. Miller

Two of the most successful methods that are presently available for simulating the quantum dynamics of condensed phase systems are centroid molecular dynamics (CMD) and ring polymer molecular dynamics (RPMD). Despite their conceptual…

Chemical Physics · Physics 2014-07-04 Mariana Rossi , Michele Ceriotti , David E. Manolopoulos

Two-dimensional Raman and hybrid terahertz/Raman spectroscopic techniques provide invaluable insight into molecular structure and dynamics of condensed-phase systems. However, corroborating experimental results with theory is difficult due…

Chemical Physics · Physics 2022-04-13 Tomislav Begušić , Xuecheng Tao , Geoffrey A. Blake , Thomas F. Miller

We present a new non-adiabatic ring polymer molecular dynamics (NRPMD) method based on the spin mapping formalism, which we refer to as the spin-mapping NRPMD (SM-NRPMD) approach. We derive the path-integral partition function expression…

Chemical Physics · Physics 2021-06-02 Duncan Bossion , Sutirtha N. Chowdhury , Pengfei Huo

The quantum thermal average plays a central role in describing the thermodynamic properties of a quantum system. Path integral molecular dynamics (PIMD) is a prevailing approach for computing quantum thermal averages by approximating the…

Numerical Analysis · Mathematics 2024-06-25 Xuda Ye , Zhennan Zhou

With the path integral approach, the thermal average in a multi-electronic-state quantum systems can be approximated by the ring polymer representation on an extended configuration space, where the additional degrees of freedom are…

Numerical Analysis · Mathematics 2020-11-24 Xiaoyu Lei , Zhennan Zhou

Yang et al. (2016) proved that the symmetric random walk Metropolis--Hastings algorithm for Bayesian variable selection is rapidly mixing under mild high-dimensional assumptions. We propose a novel MCMC sampler using an informed proposal…

Methodology · Statistics 2022-04-26 Quan Zhou , Jun Yang , Dootika Vats , Gareth O. Roberts , Jeffrey S. Rosenthal

Nonadiabatic ring-polymer molecular dynamics employs the mapping approach to describe nonadiabatic effects within the ring-polymer ansatz. In this paper, it is generalized to allow for the nuclear and electronic degrees of freedom to be…

Chemical Physics · Physics 2017-08-23 Jeremy O. Richardson , Philipp Meyer , Marc-Oliver Pleinert , Michael Thoss

Massively parallel computer architectures create new opportunities for the performance of long-timescale molecular dynamics (MD) simulations. Here, we introduce the path-accelerated molecular dynamics (PAMD) method that takes advantage of…

Computational Physics · Physics 2021-01-11 Jorge L. Rosa-Raíces , Bin Zhang , Thomas F. Miller

Path Integral Molecular Dynamics (PIMD) is a well established simulation technique to compute exact equilibrium properties for a quantum system using classical trajectories in an extended phase space. Standard PIMD simulations are…

Chemical Physics · Physics 2024-11-20 Britta A. Johnson , Siyu Bu , Christopher J. Mundy , Nandini Ananth

Bosonic exchange symmetry leads to fascinating quantum phenomena, from exciton condensation in quantum materials to the superfluidity of liquid Helium-4. Unfortunately, path integral molecular dynamics (PIMD) simulations of bosons are…

Computational Physics · Physics 2025-02-18 Yotam M. Y. Feldman , Barak Hirshberg

We derive the non-adiabatic ring polymer molecular dynamics (RPMD) approach in the phase space of the SU(N) Lie Group. This method, which we refer to as the spin mapping non-adiabatic RPMD (SM-NRPMD), is based on the spin-mapping formalism…

Chemical Physics · Physics 2023-02-15 Duncan Bossion , Sutirtha N. Chowdhury , Pengfei Huo

Quantum effects due to the spatial delocalization of light atoms are treated in molecular simulation via the path integral technique. Among several methods, Path Integral (PI) Molecular Dynamics (MD) is nowadays a powerful tool to…

Chemical Physics · Physics 2015-09-30 Animesh Agarwal , Luigi Delle Site

Ring polymer molecular dynamics (RPMD) is used to directly simulate the dynamics of an excess electron in a supercritical fluid over a broad range of densities. The accuracy of the RPMD model is tested against numerically exact path…

Statistical Mechanics · Physics 2011-07-27 Thomas F. Miller

A technique for reducing the number of integrals in a Monte Carlo calculation is introduced. For integrations relying on classical or mean-field trajectories with local weighting functions, it is possible to integrate analytically at least…

Statistical Mechanics · Physics 2024-05-17 Jarod Tall , Steven Tomsovic
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