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It is well known that fewest-switches surface hopping (FSSH) fails to correctly capture the quadratic scaling of rate constants with diabatic coupling in the weak-coupling limit, as expected from Fermi's golden rule and Marcus theory. To…

Chemical Physics · Physics 2023-11-16 Joseph E. Lawrence , Jonathan R. Mannouch , Jeremy O. Richardson

In this work, we describe various improved implementations of the mapping approach to surface hopping (MASH) for simulating nonadiabatic dynamics. These include time-reversible and piecewise-continuous integrators, which is only formally…

Chemical Physics · Physics 2026-03-31 J. Amira Geuther , Kasra Asnaashari , Jeremy O. Richardson

Trajectory surface hopping (TSH) is one of the most widely used quantum-classical algorithms for nonadiabatic molecular dynamics. Despite its empirical effectiveness and popularity, a rigorous derivation of TSH as the classical limit of a…

Chemical Physics · Physics 2013-01-11 J. M. Escartín , P. Romaniello , L. Stella , P. -G. Reinhard , E. Suraud

We implement a rare-event sampling scheme for quantifying the rate of thermally-activated nonadiabatic transitions in the condensed phase. Our QM/MM methodology uses the recently developed INAQS package to interface between an elementary…

Chemical Physics · Physics 2023-03-23 Alec J. Coffman , Zuxin Jin , Junhan Chen , Joseph E. Subotnik , D. Vale Cofer-Shabica

In this article, we propose a Frozen Gaussian Sampling (FGS) algorithm for simulating nonadiabatic quantum dynamics at metal surfaces with a continuous spectrum. This method consists of a Monte-Carlo algorithm for sampling the initial wave…

Computational Physics · Physics 2022-11-30 Zhen Huang , Limin Xu , Zhennan Zhou

A theoretical justification of the empirical surface hopping method for the laser-driven molecular dynamics is given utilizing the formalism of the exact factorization of the molecular wavefunction [Abedi et al., PRL $\textbf{105}$, 123002…

Chemical Physics · Physics 2017-07-05 T. Fiedlschuster , J. Handt , E. K. U. Gross , R. Schmidt

We present a dynamic nonlocal hybrid Monte Carlo algorithm consisting of pivot and ``cut-and-permute'' moves. The algorithm is suitable for the study of polymers in semiconfined geometries at the ordinary transition, where the pivot…

Statistical Mechanics · Physics 2007-05-23 Maria Serena Causo

The dynamic disorder model for charge carrier transport in organic semiconductors has been extensively studied in recent years. Although it is successful on determining the value of bandlike mobility in the organic crystalline materials,…

Materials Science · Physics 2012-06-21 Yao Yao , Wei Si , Xiaoyuan Hou , Chang-Qin Wu

We provide and analyze examples that counter the widely made claim that tunneling is needed for a quantum speedup in optimization problems. The examples belong to the class of perturbed Hamming-weight optimization problems. In one case,…

Quantum Physics · Physics 2016-08-23 Siddharth Muthukrishnan , Tameem Albash , Daniel A. Lidar

An extension of the CCS-method [Chem. Phys. 2004, 304, p. 103-120] for simulating non-adiabatic dynamics with quantum effects of the nuclei is put forward. The time-dependent Schr\"{o}dinger equation for the motion of the nuclei is solved…

Chemical Physics · Physics 2016-07-27 Alexander Humeniuk , Roland Mitrić

We propose a new Monte Carlo method for efficiently sampling trajectories with fixed initial and final conditions in a system with discrete degrees of freedom. The method can be applied to any stochastic process with local interactions,…

Statistical Mechanics · Physics 2012-03-30 Thierry Mora , Aleksandra M. Walczak , Francesco Zamponi

Large amplitude collective motion is investigated for a model pairing Hamiltonian containing an avoided level crossing. A classical theory of collective motion for the adiabatic limit is applied utilising either a time-dependent mean-field…

Nuclear Theory · Physics 2008-11-26 Takashi Nakatsukasa , Niels R. Walet

At present, several models for quantum computation have been proposed. Adiabatic quantum computation scheme particularly offers this possibility and is based on a slow enough time evolution of the system, where no transitions take place. In…

Quantum Physics · Physics 2012-10-12 P. J. Salas Peralta

Mixed-quantum classical (MQC) methods for simulating the dynamics of molecules at metal surfaces have the potential to accurately and efficiently provide mechanistic insight into reactive processes. Here, we introduce simple two-dimensional…

Chemical Physics · Physics 2023-08-02 James Gardner , Scott Habershon , Reinhard J. Maurer

Monte Carlo simulation is used to study the dynamical crossover from single file diffusion to normal diffusion in fluids confined to narrow channels. We show that the long time diffusion coefficients for a series of systems involving hard…

Soft Condensed Matter · Physics 2015-06-17 Surajith N. Wanasundara , Raymond J. Spiteri , Richard K. Bowles

Most experimental and theoretical studies of adiabatic optimization use stoquastic Hamiltonians, whose ground states are expressible using only real nonnegative amplitudes. This raises a question as to whether classical Monte Carlo methods…

Quantum Physics · Physics 2016-11-01 Michael Jarret , Stephen P. Jordan , Brad Lackey

We report an implementation for employing the algebraic diagrammatic construction to second order [ADC(2)] ab initio electronic structure level of theory in nonadiabatic dynamics simulations in the framework of the SHARC (surface hopping…

Chemical Physics · Physics 2019-01-11 Sebastian Mai , Felix Plasser , Mathias Pabst , Frank Neese , Andreas Köhn , Leticia González

We determine the propagation properties of a quantum particle in a d-dimensional lattice with hopping disorder, delta-correlated in time. The system is delocalized: the averaged transition probability shows a diffusive behavior. Then,…

Statistical Mechanics · Physics 2007-05-23 G. C. Ferrario , V. G. Benza

We present a preliminary surface-hopping approach for modeling intersystem crossing (ISC) dynamics between four electronic states: one singlet and one (triply degenerate) triplet. In order to incorporate all Berry force effects, the…

Chemical Physics · Physics 2022-03-29 Xuezhi Bian , Yanze Wu , Hung-Hsuan Teh , Joseph E. Subotnik

Accurate simulation the many-electronic nonadiabatic dynamics process at metal surfaces remains as a significant task. In this work, we present an orbital surface hopping (OSH) algorithm rigorously derived from the orbital quantum classical…

Chemical Physics · Physics 2025-11-24 Yong-Tao Ma , Rui-Hao Bi , Wenjie Dou