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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 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

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

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

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

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

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

In this thesis I generalize Ring Polymer Molecular Dynamics (RPMD) rate theory to electronically non-adiabatic systems, followed by application to two one-dimensional curve crossing models and a multidimensional spin-boson model.

Chemical Physics · Physics 2013-08-20 Timothy J. H. Hele

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

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

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

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

In this work, a novel ring polymer representation for multi-level quantum system is proposed for thermal average calculations. The proposed presentation keeps the discreteness of the electronic states: besides position and momentum, each…

Chemical Physics · Physics 2017-05-24 Jianfeng Lu , Zhennan Zhou

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

We describe a path-integral approach for including nuclear quantum effects in non-adiabatic chemical dynamics simulations. For a general physical system with multiple electronic energy levels, a corresponding isomorphic Hamiltonian is…

Statistical Mechanics · Physics 2018-06-05 Xuecheng Tao , Philip Shushkov , Thomas Miller

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

Mean-Field Ring Polymer Molecular Dynamics (MF-RPMD) is a powerful, efficient, and accurate method for approximate quantum dynamic simulations of multi-level system dynamics. Initial efforts to compute nonadiabatic reaction rates using…

Chemical Physics · Physics 2021-04-29 Britta Ann Johnson , Nandini Ananth

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

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

A novel approach to simulate simple protein-ligand systems at large time- and length-scales is to couple Markov state models (MSMs) of molecular kinetics with particle-based reaction-diffusion (RD) simulations, MSM/RD. Currently, MSM/RD…

Chemical Physics · Physics 2021-12-10 Mauricio J. del Razo , Manuel Dibak , Christof Schütte , Frank Noé
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