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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 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…

Statistical Mechanics · Physics 2015-06-17 Nandini Ananth

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

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

The third-order response lies at the heart of simulating and interpreting nonlinear spectroscopies ranging from two dimensional infrared (2D-IR) to 2D electronic (2D-ES), and 2D sum frequency generation (2D-SFG). The extra time and…

Chemical Physics · Physics 2022-09-21 Kenneth A. Jung , Thomas E. Markland

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 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

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

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

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

This study introduces a novel computational approach based on ratchet-and-pawl molecular dynamics (rMD) for accurately estimating ligand dissociation kinetics in protein-ligand complexes. By integrating Kramers' theory with Bell's equation,…

Chemical Physics · Physics 2025-08-19 Bruno Stegani , Riccardo Capelli

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

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

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

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

Molecular dynamics with electronic friction (MDEF) approach can describe nonadiabatic effects accurately at metal surfaces in the weak nonadiabatic limit. That being said, MDEF treats nuclear motion classically, such that the nuclear…

Chemical Physics · Physics 2024-04-09 Rui-Hao Bi , Wenjie Dou

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

To take into account nuclear quantum effects on the dynamics of atoms, the path integral molecular dynamics (PIMD) method used since 1980s is based on the formalism developed by R. P. Feynman. However, the huge computation time required for…

Computational Physics · Physics 2019-05-08 H. Dammak , M. Hayoun , F Brieuc , G. Geneste

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

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
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