Communication: Standard surface hopping predicts incorrect scaling for Marcus’ golden-rule rate: The decoherence problem cannot be ignored

Landry, Brian R.; Subotnik, Joseph E.

doi:10.1063/1.3663870

Cited by 115 publications

(176 citation statements)

References 42 publications

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“…The trajectory-based fewest switches surface hopping (FSSH) [41,42], and its variants [43][44][45][46], have thus become widely used. However, FSSH lacks a rigorous derivation, suffers from decoherence problems, and has also recently been shown to be deficient in treating isolated electron transfer due to its inability to obtain the correct scaling of Marcus' golden rule rate [47]. Several schemes have been formulated in order to attempt to solve these issues however, due to the lack of a formal derivation they simply provide ad hoc corrections [48,49].…”

Section: Introductionmentioning

confidence: 99%

Efficient and accurate surface hopping for long time nonadiabatic quantum dynamics

Kelly

Markland

2013

The Journal of Chemical Physics

105

115

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The quantum-classical Liouville equation offers a rigorous approach to nonadiabatic quantum dynamics based on surface hopping type trajectories. However, in practice the applicability of this approach has been limited to short times owing to unfavorable numerical scaling. In this paper we show that this problem can be alleviated by combining it with a formally exact generalized quantum master equation treatment. This allows dramatic improvements in the efficiency of the approach in nonadiabatic regimes, making it computationally tractable to treat the quantum dynamics of complex systems for long times. We demonstrate our approach by applying it to a model of condensed phase charge transfer where our method is shown to be numerically exact in regimes where fewest-switches surface hopping and mean field approaches fail to obtain the either the correct rates or long-time populations.

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Section: Introductionmentioning

confidence: 99%

Efficient and accurate surface hopping for long time nonadiabatic quantum dynamics

Kelly

Markland

2013

The Journal of Chemical Physics

105

115

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“…At the same time, a computationally efficient, fully classical description lacks the ability to characterize essential quantum effects. Mixed quantum-classical techniques become the only practical choice for simulating complex dynamics of electrons, [1][2][3] excitons, [4][5][6] and protons 7,8 in large systems. Such dynamics are receiving intense attention, because they govern efficiencies of many modern devices, and since they are now accessible to experimental investigation, which requires detailed theoretical interpretation.…”

mentioning

confidence: 99%

Communication: Global flux surface hopping in Liouville space

Wang

Sifain

Prezhdo

2015

The Journal of Chemical Physics

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“…As an important example of the decoherence effect, it has potential to overcome the breakdown of carrier localization, and to be able to describe the transition between the coherent and incoherent transport [47,48]. Decoherence can be brought about by the scattering effects from high-frequency intramolecular phonons [49].…”

Section: Measurement-induced Incoherent Hoppingmentioning

confidence: 99%

Charge transport in organic semiconductors: From incoherent to coherent

Yao

Yang

et al. 2013

Chin. Sci. Bull.

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Quantum decoherence in organic charge transport is a complicated but crucial topic. In this paper, several theoretical approaches corresponding to it, from incoherent to coherent, are comprehensively reviewed. We mainly focus on the physical insight provided by each theory and extent of its validity. The aim of this review is to clarify some contentious issues and elaborate on the promising perspectives provided by different approaches. The device model approaches based on both continuous and discretized treatments of the transporting layer will be first discussed. The prominent focus of this review will be devoted to the dynamic disorder model and its variants considering that it is the most promising approach to tackle charge transport problems in organic materials. We will also address other theories such as the variational method. As in all other molecular systems, the electronic coherence is an important aspect in the transport in organic semiconductors (OSCs). The phonon spectrum, consisting of both the intra-and inter-molecular ones, covers an extensive regime and makes almost all the theories about coherence inefficient. As opposed to the biomolecular systems in which the regime of interest is where the long-lived coherence exists and is thus typically specific [1], a very wide range of issues for organic semiconductors spanning completely incoherent (classical) to completely coherent (quantum) exist [2,3]. For example, to study the mobility in a given molecular system, one can utilize classical (device model [4] or kinetic Monte Carlo simulation [5]), semiclassical (surface hopping algorithm [6]), mixed quantum classical (dynamic disorder model [7] and Ehrenfest method [8]), and quantum (variational ansatz) theories. The diverse theoretical treatments make the problems obscure for experimentalists and theoreticians alike. In this review, we will briefly introduce each of these approaches and attempt to provide insights related to their applicability. The charge carriers in OSCs are recognized to be (positively or negatively) charged polarons, due to the strong self-trapping effect from lattice distortion and vibration. Polarons could be small or large, depending on the relative scales of intra-and inter-molecular interactions [9]. In a lattice model, these interactions could be described by diagonal and off-diagonal electron-phonon couplings. A typical single-carrier Hamiltonian then should be as follows [10]

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Communication: Standard surface hopping predicts incorrect scaling for Marcus’ golden-rule rate: The decoherence problem cannot be ignored

Abstract: Can we derive Tully's surface-hopping algorithm from the semiclassical quantum Liouville equation? Almost, but only with decoherence

Cited by 115 publications

References 42 publications

Efficient and accurate surface hopping for long time nonadiabatic quantum dynamics

Efficient and accurate surface hopping for long time nonadiabatic quantum dynamics

Communication: Global flux surface hopping in Liouville space

Charge transport in organic semiconductors: From incoherent to coherent

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