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To accelerate the thermal equilibrium sampling of multi-level quantum systems, the infinite swapping limit of a recently proposed multi-level ring polymer representation is investigated. In the infinite swapping limit, the ring polymer…

Chemical Physics · Physics 2018-03-14 Jianfeng Lu , Zhennan Zhou

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

An exact approach to compute physical properties for general multi-electronic-state (MES) systems in thermal equilibrium is presented. The approach is extended from our recent progress on path integral molecular dynamics (PIMD) [J. Chem.…

Chemical Physics · Physics 2017-11-22 Xinzijian Liu , Jian Liu

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

The quantum thermal average plays a central role in describing the thermodynamic properties of a quantum system. Path integral molecular dynamics (PIMD) is a prevailing approach for computing quantum thermal averages by approximating the…

Numerical Analysis · Mathematics 2024-06-25 Xuda Ye , Zhennan Zhou

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

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

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

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

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

Ring Polymer Surface-Hopping (RPSH) has been recently introduced as a well-tailored method for incorporating nuclear quantum effects (NQEs), such as zero-point energy and tunneling, into non-adiabatic molecular dynamics simulations. The…

Chemical Physics · Physics 2025-09-16 Dil K. Limbu , Farnaz A. Shakib

Recently, the mapping approach to surface hopping (MASH) was proposed as a method to simulate the non-adiabatic dynamics of two-level systems. It was shown that the method possesses many desirable qualities, both theoretically and through…

Chemical Physics · Physics 2025-07-08 Jan Vavřín

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 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

In mixed quantum-classical simulations of molecule-metal surface interactions, the discretization of the metallic electronic continuum typically results in a closed-system representation that fails to capture the open-system nature of the…

Chemical Physics · Physics 2026-03-19 Yongtao Ma , Wenjie Dou

Mixed-quantum-classical molecular dynamics simulation implies an effective measurement on the electronic states owing to continuously tracking the atomic forces.Based on this insight, we propose a quantum trajectory mean-field approach for…

Chemical Physics · Physics 2014-08-08 Wei Feng , Luting Xu , Xin-Qi Li , Weihai Fang , YiJing Yan

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

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

The powerful molecular dynamics (MD) simulation is basically based on a picture that the atoms experience classical-like trajectories under the exertion of classical force field determined by the quantum mechanically solved electronic…

Chemical Physics · Physics 2013-12-16 Wei Feng , Luting Xu , Xin-Qi Li , Weihai Fang
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