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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

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

In Part I [J. Chem. Phys. 138, 084108 (2013)] we derived a quantum transition-state theory by taking the t->0+ (short-time) limit of a new form of quantum flux-side time-correlation function containing a ring-polymer dividing surface. This…

Chemical Physics · Physics 2013-09-05 Stuart C. Althorpe , Timothy J. H. Hele

Thermal quantum time-correlation functions are of fundamental importance in quantum dynamics, allowing experimentally-measurable properties such as reaction rates, diffusion constants and vibrational spectra to be computed from first…

Chemical Physics · Physics 2017-07-25 Timothy J. H. Hele

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

We obtain thermostatted ring polymer molecular dynamics (TRPMD) from exact quantum dynamics via Matsubara dynamics, a recently-derived form of linearization which conserves the quantum Boltzmann distribution. Performing a contour integral…

Chemical Physics · Physics 2016-02-03 Timothy J. H. Hele

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…

Spatial multiscale methods have established themselves as useful tools for extending the length scales accessible by conventional statics (i.e., zero temperature molecular dynamics). Recently, extensions of these methods, such as the…

Numerical Analysis · Mathematics 2014-09-23 Andrew Binder , Mitchell Luskin , Danny Perez , Arthur F. Voter

This dissertation unifies one of the central methods of classical rate calculation, `Transition-State Theory' (TST), with quantum mechanics, thereby deriving a rigorous `Quantum Transition-State Theory' (QTST). The resulting QTST is…

Chemical Physics · Physics 2014-08-06 Timothy J. H. Hele

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

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

In a previous article [J. Chem. Phys. 138, 084108 (2013)], we showed that the $t\to 0_+$ limit of ring-polymer molecular dynamics (RPMD) rate-theory is also the $t\to 0_+$ limit of a new type of quantum flux-side time-correlation function,…

Chemical Physics · Physics 2016-05-06 Timothy J. H. Hele , Stuart C. Althorpe

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 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

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…

Chemical Physics · Physics 2025-09-16 Joseph E. Lawrence , Jeremy O. Richardson

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

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

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…

Chemical Physics · Physics 2024-05-09 Nathan London , Siyu Bu , Britta Ann Johnson , Nandini Ananth

Recently proposed non-adiabatic ring polymer molecular dynamics (NRPMD) approach has shown to provide accurate quantum dynamics by incorporating explicit electronic state descriptions and nuclear quantizations. Here, we present a rigorous…

Chemical Physics · Physics 2019-07-24 Sutirtha N. Chowdhury , Pengfei Huo
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