Benchmarking the Surface Hopping Method to Include Nuclear Quantum Effects

Sindhu, Aarti; Jain, Amber

doi:10.1021/acs.jctc.0c01065

Cited by 18 publications

(27 citation statements)

References 56 publications

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“…The model describes a dissipative quantum system and has been widely used as a benchmark for approximate nonadiabatic methods due to the feasibility of computing numerically exact quantum results. 30,32,[124][125][126][127][128][129] The spin-boson Hamiltonian can be written in the form of Eq. 2 by setting…”

Section: B Spin-boson Modelmentioning

confidence: 99%

NQCDynamics.jl: A Julia package for nonadiabatic quantum classical molecular dynamics in the condensed phase

Gardner

Douglas-Gallardo

Stark

et al. 2022

The Journal of Chemical Physics

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Accurate and efficient methods to simulate nonadiabatic and quantum nuclear effects in high-dimensional and dissipative systems are crucial for the prediction of chemical dynamics in condensed phase. To facilitate effective development, code sharing and uptake of newly developed dynamics methods, it is important that software implementations can be easily accessed and built upon.Using the Julia programming language, we have developed the \pkgname ~ package which provides a framework for established and emerging methods for performing semiclassical and mixed quantum-classical dynamics in condensed phase. The code provides several interfaces to existing atomistic simulation frameworks, electronic structure codes, and machine learning representations. In addition to the existing methods, the package provides infrastructure for developing and deploying new dynamics methods which we hope will benefit reproducibility and code sharing in the field of condensed phase quantum dynamics. Herein, we present our code design choices and the specific Julia programming features from which they benefit.We further demonstrate the capabilities of the package on two examples of chemical dynamics in condensed phase: the population dynamics of the spin-boson model as described by a wide variety of semi-classical and mixed quantum-classical nonadiabatic methods and the reactive scattering of H2 on Ag(111) using the Molecular Dynamics with Electronic Friction method. Together, they exemplify the broad scope of the package to study effective model Hamiltonians and realistic atomistic systems.

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Section: B Spin-boson Modelmentioning

confidence: 99%

NQCDynamics.jl: A Julia package for nonadiabatic quantum classical molecular dynamics in the condensed phase

Gardner

Douglas-Gallardo

Stark

et al. 2022

The Journal of Chemical Physics

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“…From a surface hopping perspective, quantum nuclear effects emerge as vibrational nonadiabaticity, i.e., avoided crossings in vibronic potential energy surfaces. As a concrete example, let us modify the Hamiltonian of eq to H = p x 2 2 m + H q m H q m = p q 2 2 m + ( true 1 / 2 m ω 1 2 q 2 V c V c 1 / 2 m ω 1 2 ( q − q 0 ) 2 + ϵ 0 ) + 1 2 m ω 2 2 false( x − italicg italicq false) 2 To treat q quantum mechanically, the vibronic adiabatic energies are calculated by solving H q m ψ i normala …”

Section: Vibrational Quantizationmentioning

confidence: 99%

“…69,70 Recent benchmarking of the surface hopping method has also been done to capture quantum nuclear effects for electronically nonadiabatic problems. 49 Simultaneous vibrational and electronic nonadiabaticity is one of the extreme cases for FSSH, where all the nuances must be treated correctly to get the correct rate constants. Including decoherence is challenging since both parallel and nonparallel surfaces are present.…”

Section: Vibrational Quantizationmentioning

confidence: 99%

Pedagogical Overview of the Fewest Switches Surface Hopping Method

Jain

Sindhu

2022

ACS Omega

Self Cite

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The fewest switches surface hopping method continues to grow in popularity to capture electronic nonadiabaticity and quantum nuclear effects due to its simplicity and accuracy. Knowing the basics of the method is essential for the correct implementation and interpretation of results. This review covers the fundamentals of the fewest switches surface hopping method with a detailed discussion of the nuances such as decoherence schemes and frustrated hops and the correct approach to calculating populations. The consequences of incorrect implementation are further discussed toward calculating kinetic and thermodynamic properties. Some tips for practitioners and a step-by-step algorithm for developers are provided. Finally, some of the finer technicalities of the fewest switches surface hopping method that are buried deep in the literature are pointed out to help graduate students better appreciate this method.

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“…The model describes a dissipative quantum system and has been widely used as a benchmark for approximate nonadiabatic methods due to the feasibility of computing numerically exact quantum results. 30,32,[123][124][125][126][127][128] The spin-boson Hamiltonian can be written in the form of Eq. 2 by setting…”

Section: B Spin-boson Modelmentioning

confidence: 99%

NQCDynamics.jl: A Julia Package for Nonadiabatic Quantum Classical Molecular Dynamics in the Condensed Phase

Gardner,

Douglas-Gallardo,

Stark

et al. 2022

Preprint

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Accurate and efficient methods to simulate nonadiabatic and quantum nuclear effects in high-dimensional and dissipative systems are crucial for the prediction of chemical dynamics in condensed phase. To facilitate effective development, code sharing and uptake of newly developed dynamics methods, it is important that software implementations can be easily accessed and built upon. Using the Julia programming language, we have developed the NQCDynamics.jl package which provides a framework for established and emerging methods for performing semiclassical and mixed quantum-classical dynamics in condensed phase. The code provides several interfaces to existing atomistic simulation frameworks, electronic structure codes, and machine learning representations. In addition to the existing methods, the package provides infrastructure for developing and deploying new dynamics methods which we hope will benefit reproducibility and code sharing in the field of condensed phase quantum dynamics. Herein, we present our code design choices and the specific Julia programming features from which they benefit. We further demonstrate the capabilities of the package on two examples of chemical dynamics in condensed phase: the population dynamics of the spin-boson model as described by a wide variety of semi-classical and mixed quantum-classical nonadiabatic methods and the reactive scattering of H 2 on Ag(111) using the Molecular Dynamics with Electronic Friction method. Together, they exemplify the broad scope of the package to study effective model Hamiltonians and realistic atomistic systems. Methods FSSH NRPMD Ehrenfest MDEF Classical Langevin eCMM Simulation Parameters Atoms Elements Masses Models Analytic model ASE calculator ML model Keywords Simulation cell Temperature Method extras Simulation Method (atoms , model; kwargs¡ ) { } FIG. 1. The user inputs required to define the parameters for a simulation. This diagram along with Figs. 2 and 3 was created using the Excalidraw 65 online tool.

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Benchmarking the Surface Hopping Method to Include Nuclear Quantum Effects

Cited by 18 publications

References 56 publications

NQCDynamics.jl: A Julia package for nonadiabatic quantum classical molecular dynamics in the condensed phase

NQCDynamics.jl: A Julia package for nonadiabatic quantum classical molecular dynamics in the condensed phase

Pedagogical Overview of the Fewest Switches Surface Hopping Method

NQCDynamics.jl: A Julia Package for Nonadiabatic Quantum Classical Molecular Dynamics in the Condensed Phase

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