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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…

化学物理 · 物理学 2021-04-28 Ivan S. Novikov , Yury V. Suleimanov , Alexander V. Shapeev

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…

化学物理 · 物理学 2017-02-08 Yury V. Suleimanov , F. Javier Aoiz , Hua Guo

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…

化学物理 · 物理学 2025-04-03 Chen Li , Liang Zhang , Bin Jiang , Hua Guo

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.…

化学物理 · 物理学 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…

化学物理 · 物理学 2017-02-08 Sergio Rampino , Yury V. Suleimanov

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…

化学物理 · 物理学 2020-01-08 Ivan S. Novikov , Alexander V. Shapeev , Yury V. Suleimanov

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…

化学物理 · 物理学 2018-11-14 Somnath Bhowmick , Duncan Bossion , Yohann Scribano , Yury V. Suleimanov

We apply Thermostatted Ring Polymer Molecular Dynamics (TRPMD), a recently-proposed approximate quantum dynamics method, to the computation of thermal reaction rates. Its short-time Transition-State Theory (TST) limit is identical to…

化学物理 · 物理学 2015-08-20 Timothy J. H. Hele , Yury V. Suleimanov

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…

化学物理 · 物理学 2022-08-18 Xiongfei Gui , Wenbin Fan , Jiace Sun , Yongle Li

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…

化学物理 · 物理学 2018-12-26 Ivan S. Novikov , Yury V. Suleimanov , Alexander V. Shapeev

In this work, rate coefficients of four prototypical insertion reactions, X + H2 -- H + XH (X=C(1D), N(2D), O(1D), S(1D)) and associated isotope reactions are calculated based on ring polymer molecular dynamics (RPMD) with Cayley propagator…

化学物理 · 物理学 2024-06-04 Wenbin Jiang , Yuhao Chen , Yongle Li

Ring-polymer molecular dynamics (RPMD) has become a popular method for describing chemical reactions due to its ability to simultaneously capture tunneling, zero-point energy, anharmonicity and recrossing. Here we highlight that despite its…

化学物理 · 物理学 2025-09-16 Joseph E. Lawrence , Jeremy O. Richardson

Mean-field Ring Polymer Molecular Dynamics (MF-RPMD) offers a computationally efficient method for the simulation of reaction rates in multi-level systems. Previous work has established that, to model a nonadiabatic state-to-state reaction…

化学物理 · 物理学 2024-05-09 Nathan London , Siyu Bu , Britta Ann Johnson , Nandini Ananth

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…

统计力学 · 物理学 2011-08-19 Artur R. Menzeleev , Nandini Ananth , Thomas F. Miller

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…

化学物理 · 物理学 2017-03-08 Kevin M. Hickson , Yury V. Suleimanov

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…

统计力学 · 物理学 2014-03-05 Artur R. Menzeleev , Franziska Bell , Thomas F. Miller

We investigate whether making the friction spatially dependent on the reaction coordinate introduces quantum effects into the thermal reaction rates for dissipative reactions. Quantum rates are calculated using the numerically exact…

A model Hamiltonian for the reaction CH$_4^+ \rightarrow$ CH$_3^+$ + H, parametrized to exhibit either early or late inner transition states, is employed to investigate the dynamical characteristics of the roaming mechanism. Tight/loose…

化学物理 · 物理学 2015-06-18 F. A. L. Mauguière , P. Collins , G. S. Ezra , S. C. Farantos , S. Wiggins

We address the calculation of microcanonical reaction rates for processes involving significant nuclear quantum effects using ring-polymer molecular dynamics (RPMD), both with and without electronically non-adiabatic transitions. After…

统计力学 · 物理学 2020-04-22 Xuecheng Tao , Philip Shushkov , 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…

统计力学 · 物理学 2015-06-17 Nandini Ananth
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