A size-consistent multi-state mapping approach to surface hopping

Lawrence, Joseph E.; Mannouch, Jonathan R.; Richardson, Jeremy O.

doi:10.1063/5.0208575

The Journal of Chemical Physics

2024

DOI: 10.1063/5.0208575

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A size-consistent multi-state mapping approach to surface hopping

Joseph E. Lawrence,

Jonathan R. Mannouch,

Jeremy O. Richardson

Abstract: We develop a multi-state generalization of the recently proposed mapping approach to surface hopping (MASH) for the simulation of electronically nonadiabatic dynamics. This new approach extends the original MASH method to be able to treat systems with more than two electronic states. It differs from previous approaches in that it is size consistent and rigorously recovers the original two-state MASH in the appropriate limits. We demonstrate the accuracy of the method by applying it to a series of model systems… Show more

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Cited by 4 publications

References 98 publications

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Toward a Correct Description of Initial Electronic Coherence in Nonadiabatic Dynamics Simulations

Mannouch,

Kelly

2024

J. Phys. Chem. Lett.

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The recent improvement in experimental capabilities for interrogating and controlling molecular systems with ultrafast coherent light sources calls for the development of theoretical approaches that can accurately and efficiently treat electronic coherence. However, the most popular and practical nonadiabatic molecular dynamics techniques, Tully's fewest-switches surface hopping and Ehrenfest mean-field dynamics, are unable to describe the dynamics proceeding from an initial electronic coherence. While such issues are not encountered with the analogous coupledtrajectory algorithms or numerically exact quantum dynamics methods, applying such techniques necessarily comes with a higher computational cost. Here we show that a correct description of initial electronic coherence can indeed be achieved using independent-trajectory methods derived from the semiclassical mapping formalism. The key is the introduction of an initial sampling over the electronic phase space and a means of incorporating phase interference between trajectories, both of which are naturally achieved when working within the semiclassical mapping framework.

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Toward a Correct Description of Initial Electronic Coherence in Nonadiabatic Dynamics Simulations

Mannouch,

Kelly

2024

J. Phys. Chem. Lett.

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A MASH simulation of the photoexcited dynamics of cyclobutanone

Lawrence,

Ansari,

Mannouch

et al. 2024

The Journal of Chemical Physics

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In response to a community prediction challenge, we simulate the nonadiabatic dynamics of cyclobutanone using the mapping approach to surface hopping (MASH). We consider the first 500 fs of relaxation following photoexcitation to the S2 state and predict the corresponding time-resolved electron-diffraction signal that will be measured by the planned experiment. 397 ab initio trajectories were obtained on the fly with state-averaged complete active space self-consistent field using a (12,11) active space. To obtain an estimate of the potential systematic error, 198 of the trajectories were calculated using an aug-cc-pVDZ basis set and 199 with a 6-31+G* basis set. MASH is a recently proposed independent trajectory method for simulating nonadiabatic dynamics, originally derived for two-state problems. As there are three relevant electronic states in this system, we used a newly developed multi-state generalization of MASH for the simulation: the uncoupled spheres multi-state MASH method (unSMASH). This study, therefore, serves both as an investigation of the photodissociation dynamics of cyclobutanone, and also as a demonstration of the applicability of unSMASH to ab initio simulations. In line with previous experimental studies, we observe that the simulated dynamics is dominated by three sets of dissociation products, C3H6 + CO, C2H4 + C2H2O, and C2H4 + CH2 + CO, and we interpret our predicted electron-diffraction signal in terms of the key features of the associated dissociation pathways.

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Charge transport in organic semiconductors from the mapping approach to surface hopping

Runeson,

Drayton,

Manolopoulos

2024

The Journal of Chemical Physics

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We describe how to simulate charge diffusion in organic semiconductors using a recently introduced mixed quantum–classical method, the mapping approach to surface hopping. In contrast to standard fewest-switches surface hopping, this method propagates the classical degrees of freedom deterministically on the most populated adiabatic electronic state. This correctly preserves the equilibrium distribution of a quantum charge coupled to classical phonons, allowing one to time-average along trajectories to improve the statistical convergence of the calculation. We illustrate the method with an application to a standard model for the charge transport in the direction of maximum mobility in crystalline rubrene. Because of its consistency with the equilibrium distribution, the present method gives a time-dependent diffusion coefficient that plateaus correctly to a long-time limiting value. The resulting mobility is somewhat higher than that of the relaxation time approximation, which uses a phenomenological relaxation parameter to obtain a non-zero diffusion coefficient from a calculation with static phonon disorder. However, it is very similar to the mobility obtained from Ehrenfest dynamics, at least in the parameter regimes we have investigated here. This is somewhat surprising because Ehrenfest dynamics overheats the electronic subsystem and is, therefore, inconsistent with the equilibrium distribution.

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A size-consistent multi-state mapping approach to surface hopping

Cited by 4 publications

References 98 publications

Toward a Correct Description of Initial Electronic Coherence in Nonadiabatic Dynamics Simulations

Toward a Correct Description of Initial Electronic Coherence in Nonadiabatic Dynamics Simulations

A MASH simulation of the photoexcited dynamics of cyclobutanone

Charge transport in organic semiconductors from the mapping approach to surface hopping

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