Ring polymer molecular dynamics and active learning of moment tensor potential for gas-phase barrierless reactions: Application to S + H2.

  title={Ring polymer molecular dynamics and active learning of moment tensor potential for gas-phase barrierless reactions: Application to S + H2.},
  author={Ivan S. Novikov and Alexander V. Shapeev and Yury V. Suleimanov},
  journal={The Journal of chemical physics},
  volume={151 22},
Ring polymer molecular dynamics (RPMD) has proven to be an accurate approach for calculating thermal rate coefficients of various chemical reactions. For wider application of this methodology, efficient ways to generate the underlying full-dimensional potential energy surfaces (PESs) and the corresponding energy gradients are required. Recently, we have proposed a fully automated procedure based on combining the original RPMDrate code with active learning for PES on-the-fly using moment tensor… 

Figures and Tables from this paper

Making thermal rate constant calculations reliable using best practices: case study of OH + HBr $\to$ Br + H$_2$O
In the present work we apply the combination of Moment Tensor Potential (MTP) and Ring Polymer Molecular Dynamics (RPMD) to the calculation of the thermal rate constants of the OH + HBr → Br + H 2 O
Kinetics theoretical study of the O(3P) + C2H6 reaction on an ab initio-based global potential energy surface
Based on a recently developed analytical full-dimensional potential energy surface describing the gas-phase O(3P) + C2H6 reaction (Espinosa-Garcia et al. in Phys Chem Chem Phys 22:22,591, 2020),
VTST and RPMD kinetics study of the nine-body X + C2H6 (X ≡ H, Cl, F) reactions based on analytical potential energy surfaces.
Thermal rate constants of nine-atom hydrogen abstraction reactions have been investigated using two kinetics approaches - variational transition state theory with multidimensional tunnelling and ring polymer molecular dynamics (RPMD) and full dimensional analytical potential energy surfaces and available experimental information shows discrepancies.
Machine learning-assisted approximation of symmetrized quantum time correlation functions
Open-chain imaginary-time path-integral sampling approach known with the acronym OPSCF (J. Chem. Phys. 148, 102340 (2018)) is an approach to the calculation of approximate symmetrized quantum time
The MLIP package: moment tensor potentials with MPI and active learning
This paper illustrates how to construct moment tensor potentials using active learning as implemented in the MLIP package, focusing on the efficient ways to automatically sample configurations for the training set, and how expanding theTraining set changes the error of predictions.
Dynamical strengthening of covalent and non-covalent molecular interactions by nuclear quantum effects at finite temperature
Evidence is presented that NQE often enhance electronic interactions and, in turn, can result in dynamical molecular stabilization at finite temperature, which yields new insights into the versatile role of nuclear quantum fluctuations in molecules and materials.
Couplings for Andersen dynamics
  • N. Bou-Rabee, A. Eberle
  • Mathematics
    Annales de l'Institut Henri Poincaré, Probabilités et Statistiques
  • 2022
Andersen dynamics is a standard method for molecular simulations, and a precursor of the Hamiltonian Monte Carlo algorithm used in MCMC inference. The stochastic process corresponding to Andersen
microscopic derivation of coupled SPDE’s with a
. This paper is concerned with the relationship between forward–backward stochastic Volterra integral equations (FBSVIEs, for short) and a system of (nonlocal in time) path dependent partial
On-the-Fly Active Learning of Interatomic Potentials for Large-Scale Atomistic Simulations.
The on-the-fly generation of machine-learning force fields by active-learning schemes is demonstrated by presenting recent applications and overall, simulations are accelerated by several orders of magnitude while retaining almost first-principles accuracy.


Ring polymer molecular dynamics fast computation of rate coefficients on accurate potential energy surfaces in local configuration space: Application to the abstraction of hydrogen from methane.
A segmented strategy for fitting suitable potential energy surface (PES) on which ring-polymer molecular dynamics (RPMD) simulations are performed, on which qualitative agreement between present RPMD rates and those from previous simulations as well as experimental results are found.
Bimolecular reaction rates from ring polymer molecular dynamics: application to H + CH4 → H2 + CH3.
The results indicate that the previous assessment of the accuracy of the RPMD approximation for atom-diatom reactions remains valid for more complex polyatomic reactions, and suggest that the sensitivity of the QTST and QI rate coefficients to the choice of the transition state dividing surface becomes more of an issue as the dimensionality of the reaction increases.
Communication: Rate coefficients of the H + CH4 → H2 + CH3 reaction from ring polymer molecular dynamics on a highly accurate potential energy surface.
The present RPMD rates are in excellent agreement with quantum rates computed on the same potential energy surface, as well as with the experimental measurements, demonstrating further that the RPMD is capable of producing accurate rates for polyatomic chemical reactions even at rather low temperatures.
Ring-polymer molecular dynamics: rate coefficient calculations for energetically symmetric (near thermoneutral) insertion reactions (X + H2) → HX + H(X = C(1D), S(1D)).
For both chemical reactions, RPMD displays remarkable accuracy and agreement with the previous quantum dynamic results that make it encouraging for the future application of the RPMD to other barrier-less, complex-forming reactions involving polyatomic reactants with any exothermicity.
Chemical reaction rates from ring polymer molecular dynamics.
The ring-polymer molecular dynamics method can be adapted to calculate approximate Kubo-transformed flux-side correlation functions, and hence rate coefficients for condensed phase reactions, and it gives the exact quantum-mechanical rate constant for the transmission through a parabolic barrier.
Ring-Polymer Molecular Dynamics Rate Coefficient Calculations for Insertion Reactions: X + H2 → HX + H (X = N, O).
It is shown that the unique ability of the RPMD approach among the existing theoretical methods to capture the quantum effects, e.g., tunneling and zero-point energy, as well as recrossing dynamics quantum mechanically with ring-polymer trajectories leads to excellent agreement with rigorous quantum dynamics calculations.
A refined ring polymer molecular dynamics theory of chemical reaction rates.
The long-time limit of the new flux-side correlation function, and hence the fully converged RPMD reaction rate, is rigorously independent of the choice of the transition state dividing surface, which is especially significant because the optimum dividing surface can often be very difficult to determine for reactions in complex chemical systems.
Thermal Rate Coefficients for the Astrochemical Process C + CH+ → C2+ + H by Ring Polymer Molecular Dynamics.
There is a significant discrepancy between the RPMD rate coefficients and the previous theoretical results that can lead to overestimation of the rate coefficients for the title reaction by several orders of magnitude at very low temperatures.
Ring-Polymer Molecular Dynamics for the Prediction of Low-Temperature Rates: An Investigation of the C((1)D) + H2 Reaction.
The ring-polymer molecular dynamics method is proposed as an accurate and efficient alternative for determining the kinetics and dynamics of a wide range of low-temperature reactions by analyzing the behavior of the barrierless C((1)D) + H2 reaction over the two lowest singlet potential energy surfaces.
Bimolecular reaction rates from ring polymer molecular dynamics.
We describe an efficient procedure for calculating the rates of bimolecular chemical reactions in the gas phase within the ring polymer molecular dynamics approximation. A key feature of the