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The accurate and efficient calculation of the rate coefficients of chemical reactions is a key issue in the research of chemical dynamics. In this work, by applying the dimension-free ultra-stable Cayley propagator, the thermal rate…

Chemical Physics · Physics 2022-08-18 Xiongfei Gui , Wenbin Fan , Jiace Sun , Yongle Li

The ring-polymer molecular dynamics (RPMD) was used to calculate the thermal rate coefficients of the two-channel roaming reaction H + MgH. Both reaction channels, tight and roaming, are explicitly considered. This is a pioneering attempt…

Chemical Physics · Physics 2021-05-26 Hui Yang , Wenbin Fan , Junhua Fang , Jianing Song , Yongle Li

The ring polymer molecular dynamics (RPMD) rate theory is an efficient and accurate method for estimating rate coefficients of chemical reactions affected by nuclear quantum effects. The commonly used RPMD treatment of gas-phase bimolecular…

Chemical Physics · Physics 2025-04-03 Chen Li , Liang Zhang , Bin Jiang , Hua Guo

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…

Chemical Physics · Physics 2020-01-08 Ivan S. Novikov , Alexander V. Shapeev , Yury V. Suleimanov

Ring polymer molecular dynamics (RPMD) is an accurate method for calculating thermal chemical reaction rates. It has recently been discovered that low-temperature calculations are strongly affected by the simulation parameters. Here, for…

Chemical Physics · Physics 2021-04-28 Ivan S. Novikov , Yury V. Suleimanov , Alexander V. Shapeev

The reaction between D$^+$ and H$_2$ plays an important role in astrochemistry at low temperatures and also serves as a prototype for simple ion-molecule reaction. Its ground $\tilde{X}~^1A^{\prime}$ state has a very small thermodynamic…

Chemical Physics · Physics 2018-11-14 Somnath Bhowmick , Duncan Bossion , Yohann Scribano , Yury V. Suleimanov

Globally accurate full-dimensional ground state potential energy surface (PES) for the Cl($^2$P) + XCl $\to$ HCl + Cl($^2$P) reaction, a prototypical heavy-light-heavy abstract reaction, is developed using permutation invariant polynomial…

Chemical Physics · Physics 2023-07-26 Qiang Li , Mingjuan Yang , Hongwei Song , Yongle Li

In a previous joint experimental and theoretical study of the barrierless chemical reaction C(1D) + H2 at low temperatures (300-50 K) [K. M. Hickson, J.-C. Loison, H. Guo, Y. V. Suleimanov, J. Phys. Chem. Lett., 2015, 6, 4194.], excellent…

Chemical Physics · Physics 2017-03-08 Kevin M. Hickson , Yury V. Suleimanov

This Feature Article presents an overview of the current status of Ring Polymer Molecular Dynamics (RPMD) rate theory. We first analyze the RPMD approach and its connection to quantum transition-state theory. We then focus on its practical…

Chemical Physics · Physics 2017-02-08 Yury V. Suleimanov , F. Javier Aoiz , Hua Guo

Accurately modeling gas-surface collision dynamics presents a great challenge for theory, especially in the low energy (or temperature) regime where quantum effects are important. Here, a path integral based non-equilibrium ring polymer…

Chemical Physics · Physics 2019-12-06 Qinghua Liu , Liang Zhang , Yongle Li , Bin Jiang

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

We combined Moment Tensor Potential (MTP) and Ring Polymer Molecular Dynamics (RPMD) for calculating the thermal rate constants of the OH + HBr system. We used the active learning (AL) algorithm for constructing a training set during RPMD.…

Chemical Physics · Physics 2024-09-09 Ivan S. Novikov , Edgar M. Makarov , Alexander V. Shapeev , Yury V. Suleimanov

Thermal rate coefficients for the astrochemical reaction C + CH$^+$ $\to$ C$_2^+$ + H were computed in the temperature range 20-300 K by using novel rate theory based on ring polymer molecular dynamics (RPMD) on a recently published…

Chemical Physics · Physics 2017-02-08 Sergio Rampino , Yury V. Suleimanov

Temperature dependence of the thermal rate constants and kinetic isotope effects (KIE) of the CN + C2H6 gas-phase hydrogen abstraction reaction was theoretically determined within the 25-1000 K temperature range, i.e., from ultra-low to…

Chemical Physics · Physics 2024-03-05 Joaquin Espinosa-Garcia , Somnath Bhowmick

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

We propose a methodology for fully automated calculation of thermal rate coefficients of gas phase chemical reactions, which is based on combining the ring polymer molecular dynamics (RPMD) with the machine-learning interatomic potentials…

Chemical Physics · Physics 2018-12-26 Ivan S. Novikov , Yury V. Suleimanov , Alexander V. Shapeev

We report combined studies on the prototypical S(^1D_2) + H2 insertion reaction. Kinetics and crossed-beam experiments are performed in experimental conditions approaching the cold energy regime, yielding absolute rate coefficients down to…

Time-dependent wave packet calculations for the reaction H+HCl and its isotopic reactions are carried out on the potential energy surface (PES) of Bian and Werner (BW2) [Bian, W.; Werner, H. -J., J. Chem. Phys. 2000, 112, 220]. Reaction…

Chemical Physics · Physics 2007-05-23 Li Yao , Ke-Li Han , He-Shan Song , Dong-Hui Zhang

The use of ring polymer molecular dynamics (RPMD) for the direct simulation of electron transfer (ET) reaction dynamics is analyzed in the context of Marcus theory, semiclassical instanton theory, and exact quantum dynamics approaches. For…

Statistical Mechanics · Physics 2011-08-19 Artur R. Menzeleev , Nandini Ananth , Thomas F. Miller

The exact formulation of the path integral centroid dynamics is extended to include composites of the position and momentum operators. We present the generalized centroid dynamics (GCD), which provides a basis to calculate Kubo-transformed…

Quantum Physics · Physics 2014-01-28 Atsushi Horikoshi
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