Surface hopping
View article: Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics
Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics Open
Nonadiabatic mixed quantum-classical (NA-MQC) dynamics methods form a class of computational theoretical approaches in quantum chemistry tailored to investigate the time evolution of nonadiabatic phenomena in molecules and supramolecular a…
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Ab Initio Nonadiabatic Quantum Molecular Dynamics Open
The Born-Oppenheimer approximation underlies much of chemical simulation and provides the framework defining the potential energy surfaces that are used for much of our pictorial understanding of chemical phenomena. However, this approxima…
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Nonadiabatic dynamics: The SHARC approach Open
We review the Surface Hopping including ARbitrary Couplings (SHARC) approach for excited‐state nonadiabatic dynamics simulations. As a generalization of the popular surface hopping method, SHARC allows simulating the full‐dimensional dynam…
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Understanding the Surface Hopping View of Electronic Transitions and Decoherence Open
We present a current, up-to-date review of the surface hopping methodology for solving nonadiabatic problems, 25 years after Tully published the fewest switches surface hopping algorithm. After reviewing the original motivation for and fai…
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Nonadiabatic Excited-State Dynamics with Machine Learning Open
We show that machine learning (ML) can be used to accurately reproduce nonadiabatic excited-state dynamics with decoherence-corrected fewest switches surface hopping in a 1-D model system. We propose to use ML to significantly reduce the s…
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On-the-Fly CASPT2 Surface-Hopping Dynamics Open
We report the development of programs for on-the-fly surface-hopping dynamics simulations in the gas and condensed phases on the potential energy surfaces computed by multistate multireference perturbation theory (XMS-CASPT2) with full int…
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Highly efficient surface hopping dynamics using a linear vibronic coupling model Open
A highly efficient protocol for performing nonadiabatic dynamics simulations is implemented and applied to ultrafast internal conversion and intersystem crossing in various molecules.
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Benzophenone Ultrafast Triplet Population: Revisiting the Kinetic Model by Surface-Hopping Dynamics Open
The photochemistry of benzophenone, a paradigmatic organic molecule for photosensitization, was investigated by means of surface-hopping ab initio molecular dynamics. Different mechanisms were found to be relevant within the first 600 fs a…
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Different flavors of nonadiabatic molecular dynamics Open
The Born‐Oppenheimer approximation constitutes a cornerstone of our understanding of molecules and their reactivity, partly because it introduces a somewhat simplified representation of the molecular wavefunction . However, when a molecule…
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Newton-X Platform: New Software Developments for Surface Hopping and Nuclear Ensembles Open
Newton-X is an open-source computational platform to perform nonadiabatic molecular dynamics based on surface hopping and spectrum simulations using the nuclear ensemble approach. Both are among the most common methodologies in computation…
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Crossover from Hopping to Band-Like Charge Transport in an Organic Semiconductor Model: Atomistic Nonadiabatic Molecular Dynamics Simulation Open
The mechanism of charge transport (CT) in a 1D atomistic model of an organic semiconductor is investigated using surface hopping nonadiabatic molecular dynamics. The simulations benefit from a newly implemented state tracking algorithm tha…
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Elucidating the Nuclear Quantum Dynamics of Intramolecular Double Hydrogen Transfer in Porphycene Open
We address the double hydrogen transfer (DHT) dynamics of the porphycene molecule, a complex paradigmatic system in which the making and breaking of H-bonds in a highly anharmonic potential energy surface require a quantum mechanical treat…
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Ultrafast Photoinduced Dynamics of 1,3-Cyclohexadiene Using XMS-CASPT2 Surface Hopping Open
A full-dimensional simulation of the photodissociation of 1,3-cyclohexadiene in the manifold of three electronic states was performed via nonadiabatic surface hopping dynamics using extended multistate complete active space second-order pe…
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A mapping approach to surface hopping Open
We present a nonadiabatic classical-trajectory approach that offers the best of both worlds between fewest-switches surface hopping (FSSH) and quasiclassical mapping dynamics. This mapping approach to surface hopping (MASH) propagates the …
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Dynamics in reactions on metal surfaces: A theoretical perspective Open
Recent advances in theoretical characterization of reaction dynamics on metal surfaces are reviewed. It is shown that the widely available density functional theory of metals and their interactions with molecules have enabled first princip…
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Assessing the performance of trajectory surface hopping methods: Ultrafast internal conversion in pyrazine Open
Trajectory surface hopping (TSH) methods have been widely used to study photoinduced nonadiabatic processes. In the present study, nonadiabatic dynamics simulations with the widely used Tully’s fewest switches surface hopping (FSSH) algori…
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Surface Hopping Dynamics on Vibronic Coupling Models Open
The simulation of photoinduced non-adiabatic dynamics is of great relevance in many scientific disciplines, ranging from physics and materials science to chemistry and biology. Upon light irradiation, different relaxation processes take pl…
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Detailed balance, internal consistency, and energy conservation in fragment orbital-based surface hopping Open
We have recently introduced an efficient semi-empirical non-adiabatic molecular dynamics method for the simulation of charge transfer/transport in molecules and molecular materials, denoted fragment orbital-based surface hopping (FOB-SH) […
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Strong Influence of Decoherence Corrections and Momentum Rescaling in Surface Hopping Dynamics of Transition Metal Complexes Open
The reliability of different parameters in the surface hopping method is assessed for a vibronic coupling model of a challenging transition metal complex, where a large number of electronic states of different multiplicities are met within…
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Nonadiabatic Dynamics Algorithms with Only Potential Energies and Gradients: Curvature-Driven Coherent Switching with Decay of Mixing and Curvature-Driven Trajectory Surface Hopping Open
Direct dynamics by mixed quantum-classical nonadiabatic methods is an important tool for understanding processes involving multiple electronic states. Very often, the computational bottleneck of such direct simulation comes from electronic…
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Nonadiabatic Dynamics of Cycloparaphenylenes with TD-DFTB Surface Hopping Open
We implemented a version of the decoherence-corrected fewest switches surface hopping based on linear-response time-dependent density functional tight binding (TD-DFTB), enhanced by transition density analysis. The method has been tested f…
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Enigmatic HCl + Au(111) Reaction: A Puzzle for Theory and Experiment Open
The reactive scattering of HCl on Au(111) is currently one of the most peculiar reactions in the field of surface chemistry, as it so far eludes an accurate theoretical description. Possible reasons for the observed mismatch between theory…
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Photochemistry in the strong coupling regime: A trajectory surface hopping scheme Open
The strong coupling regime between confined light and organic molecules turned out to be promising in modifying both the ground state and the excited states properties. Under this peculiar condition, the electronic states of the molecule a…
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Classical Force Fields Tailored for QM Applications: Is It Really a Feasible Strategy? Open
Classical molecular dynamics is more and more often coupled to quantum mechanical based techniques as a statistical tool to sample configurations of molecular systems embedded in complex environments. Nonetheless, the classical potentials …
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Dynamics of Azobenzene Dimer Photoisomerization: Electronic and Steric Effects Open
While azobenzenes readily photoswitch in solution, their photoisomerization in densely packed self-assembled monolayers (SAMs) can be suppressed. Reasons for this can be steric hindrance and/or electronic quenching, e.g., by exciton coupli…
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Dissociative Chemisorption of O<sub>2</sub> on Al(111): Dynamics on a Correlated Wave-Function-Based Potential Energy Surface Open
Dissociative chemisorption of O2 on the Al(111) surface represents an extensively studied prototype for understanding the interaction between O2 and metal surfaces. It is well known that the experimentally observed activation barrier for O…
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A multi-state mapping approach to surface hopping Open
We describe a multiple electronic state adaptation of the mapping approach to surface hopping introduced recently by Mannouch and Richardson [J. Chem. Phys. 158, 104111 (2023)]. Our modification treats populations and coherences on an equa…
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How to calculate charge mobility in molecular materials from surface hopping non-adiabatic molecular dynamics – beyond the hopping/band paradigm Open
We present an efficient surface hopping approach tailored to study charge transport in high mobility organic semiconductors and discuss key improvements with regard to decoherence, trivial crossings and spurious charge transfer.
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An exact factorization perspective on quantum interferences in nonadiabatic dynamics Open
Nonadiabatic quantum interferences emerge whenever nuclear wavefunctions in different electronic states meet and interact in a nonadiabatic region. In this work, we analyze how nonadiabatic quantum interferences translate in the context of…
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Multistate hybrid time-dependent density functional theory with surface hopping accurately captures ultrafast thymine photodeactivation Open
We report an efficient analytical implementation of first-order nonadiabatic derivative couplings between arbitrary Born–Oppenheimer states in the hybrid time-dependent density functional theory (TDDFT) framework using atom-centered basis …