Nonadiabatic effects on the charge transfer rate constant: A numerical study of a simple model system

Shin, Seokmin; Metiu, Horia

doi:10.1063/1.468795

Cited by 151 publications

(156 citation statements)

References 58 publications

(41 reference statements)

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“…We study here the 1D Shin-Metiu model 76 for non-adiabatic electron transfer. The system consists of three ions and a single electron, as depicted in Fig.…”

Section: Non-adiabatic Electron Transfermentioning

confidence: 99%

The exact forces on classical nuclei in non-adiabatic charge transfer

Agostini

Abedi

Suzuki

et al. 2015

The Journal of Chemical Physics

110

195

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Non-adiabatic processes in the charge transfer reaction of O2 molecules with potassium surfaces without dissociation J. Chem. Phys. 141, 074711 (2014) The exact forces on classical nuclei in non-adiabatic charge transfer The decomposition of electronic and nuclear motion presented in Abedi et al. [Phys. Rev. Lett. 105, 123002 (2010)] yields a time-dependent potential that drives the nuclear motion and fully accounts for the coupling to the electronic subsystem. Here, we show that propagation of an ensemble of independent classical nuclear trajectories on this exact potential yields dynamics that are essentially indistinguishable from the exact quantum dynamics for a model non-adiabatic charge transfer problem. We point out the importance of step and bump features in the exact potential that are critical in obtaining the correct splitting of the quasiclassical nuclear wave packet in space after it passes through an avoided crossing between two Born-Oppenheimer surfaces and analyze their structure. Finally, an analysis of the exact potentials in the context of trajectory surface hopping is presented, including preliminary investigations of velocity-adjustment and the force-induced decoherence effect. C 2015 AIP Publishing LLC.[http://dx

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“…We study here the 1D Shin-Metiu model 76 for non-adiabatic electron transfer. The system consists of three ions and a single electron, as depicted in Fig.…”

Section: Non-adiabatic Electron Transfermentioning

confidence: 99%

The exact forces on classical nuclei in non-adiabatic charge transfer

Agostini

Abedi

Suzuki

et al. 2015

The Journal of Chemical Physics

110

195

View full text Add to dashboard Cite

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“…The nonadiabatic quantum dynamics investigated in the present work is based on the 1D Shin-Metiu model 89 for nonadiabatic electron transfer. The system consists of three ions and a single electron, as depicted in Fig.…”

Section: A Proton-coupled Electron Transfer Modelmentioning

confidence: 99%

An exact factorization perspective on quantum interferences in nonadiabatic dynamics

Curchod

Agostini

Gross

2016

The Journal of Chemical Physics

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The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. 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 the exact factorization of the molecular wavefunction. In particular, we focus our attention on the shape of the time-dependent potential energy surface-the exact surface on which the nuclear dynamics takes place. We use a one-dimensional exactly solvable model to reproduce different conditions for quantum interferences, whose characteristic features already appear in one-dimension. The time-dependent potential energy surface develops complex features when strong interferences are present, in clear contrast to the observed behavior in simple nonadiabatic crossing cases. Nevertheless, independent classical trajectories propagated on the exact time-dependent potential energy surface reasonably conserve a distribution in configuration space that mimics one of the exact nuclear probability densities. Published by AIP Publishing.[http://dx

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“…These long-time oscillations arise because some of the initial wavepacket is transferred to and trapped in the upper adiabatic surface before leaking out to the product side of the lower surface at later times. The reaction probability clearly shows the signature of resonance structure [25,26], reflecting such trapping on the upper surface. The time-dependence of diabatic wavefunctions also exhibits interesting behavior (Fig.…”

Section: Application To Model Nonadiabatic Reactionsmentioning

confidence: 95%