Confronting surface hopping molecular dynamics with Marcus theory for a molecular donor–acceptor system

Spencer, Jacob; Scalfi, Laura; Carof, Antoine; Blumberger, Jochen

doi:10.1039/c6fd00107f

Cited by 30 publications

(57 citation statements)

References 51 publications

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“…(15c), the electronic coupling is much smaller than the reorganization free energy (λ H ab ). 86 This finally means that (λ + ∆G 0 ) |H ab | 2 1/2 TS and thus the full semiclassical LZ rate equation reduces to 35…”

Section: Adiabatic and Non-adiabatic Limitmentioning

confidence: 98%

“…Consequently, in this limit the electronic transmission coefficient κ el approaches unity, which reduces the semi-classical TST expression, eq. (13), to a standard Arrhenius form 35,86…”

Section: Adiabatic and Non-adiabatic Limitmentioning

confidence: 99%

“…(14). For a vanishing driving force ∆G 0 = 0 and under the assumption that the mean square coupling elements averaged in the TS and the initial state agree, |H ab | 2 = |H ab | 2 TS = |H ab | 2 a , the barrier height is then given by a simple quadratic equation 86…”

Section: Adiabatic and Non-adiabatic Limitmentioning

confidence: 99%

“…94 In a more approximate approach geared towards on-thefly determination of charge transfer parameters in a direct charge propagation model (see Sec. 5.3.4 below), Spencer et al 86,93 determined on-site energies purely from classical force field calculations. Finally, Nagata 102 pioneered the use of a fitted charge response kernel 103 to determine on-site energy disorder in amorphous Tris(8-hydroxyquinolinato)aluminium.…”

Section: On-site Energiesmentioning

confidence: 99%

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Charge Transport in Molecular Materials: An Assessment of Computational Methods

2017

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The booming field of molecular electronics has fostered a surge of computational research on electronic properties of organic molecular solids. In particular, with respect to a microscopic understanding of transport and loss mechanisms, theoretical studies assume an ever-increasing role. Owing to the tremendous diversity of organic molecular materials, a great number of computational methods have been put forward to suit every possible charge transport regime, material, and need for accuracy. With this review article we aim at providing a compendium of the available methods, their theoretical foundations, and their ranges of validity. We illustrate these through applications found in the literature. The focus is on methods available for organic molecular crystals, but mention is made wherever techniques are suitable for use in other related materials such as disordered or polymeric systems.

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Section: Adiabatic and Non-adiabatic Limitmentioning

confidence: 98%

“…Consequently, in this limit the electronic transmission coefficient κ el approaches unity, which reduces the semi-classical TST expression, eq. (13), to a standard Arrhenius form 35,86…”

Section: Adiabatic and Non-adiabatic Limitmentioning

confidence: 99%

Section: Adiabatic and Non-adiabatic Limitmentioning

confidence: 99%

Section: On-site Energiesmentioning

confidence: 99%

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Charge Transport in Molecular Materials: An Assessment of Computational Methods

2017

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“…T 3 (15) and the data fitted appropriately. In all these cases, the decay times for the forward reaction were compared although for Eq.…”

Section: Resultsmentioning

confidence: 91%

Strong Influence of Decoherence Corrections and Momentum Rescaling in Surface Hopping Dynamics of Transition Metal Complexes

Plasser¹,

Mai²,

Fumanal³

et al. 2019

Preprint

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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 a small energy range. In particular, the effect of two decoherence correction schemes and of various strategies for momentum rescaling and treating frustrating hops during the dynamics is investigated and compared against an accurate quantum dynamics simulation. The results show that small differences in the surface hopping protocol can strongly affect the results. We find a clear preference for momentum rescaling along the nonadiabatic coupling vector and trace this effect back to an enhanced number of frustrated hops. Furthermore, reflection of the momentum after frustrated hops is shown to work better than to ignore the process completely. The study also highlights the importance of the decoherence correction but neither of the two methods employed, energy based decoherence and augmented fewest switches surface hopping, performs completely satisfactory. More generally, the study emphasises the importance of the often neglected parameters in surface hopping and shows that there is still need for simple, robust, and generally applicable correction schemes.

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Impact of Nanoscale Morphology on Charge Carrier Delocalization and Mobility in an Organic Semiconductor

et al. 2021

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A central challenge of organic semiconductor research is to make cheap, disordered materials that exhibit high electrical conductivity. Unfortunately, this endeavor is hampered by the poor fundamental understanding of the relationship between molecular packing structure and charge carrier mobility. Here a novel computational methodology is presented that fills this gap. Using a melt‐quench procedure it is shown that amorphous pentacene spontaneously self‐assembles to nanocrystalline structures that, at long quench times, form the characteristic herringbone layer of the single crystal. Quantum dynamical simulations of electron hole transport show a clear correlation between the crystallinity of the sample, the quantum delocalization, and the mobility of the charge carrier. Surprisingly, the long‐held belief that charge carriers form relatively localized polarons in disordered OS is only valid for fully amorphous structures—for nanocrystalline and crystalline samples, significant charge carrier delocalization over several nanometers occurs that underpins their improved conductivities. The good agreement with experimentally available data makes the presented methodology a robust computational tool for the predictive engineering of disordered organic materials.

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Confronting surface hopping molecular dynamics with Marcus theory for a molecular donor–acceptor system

Cited by 30 publications

References 51 publications

Charge Transport in Molecular Materials: An Assessment of Computational Methods

Charge Transport in Molecular Materials: An Assessment of Computational Methods

Strong Influence of Decoherence Corrections and Momentum Rescaling in Surface Hopping Dynamics of Transition Metal Complexes

Impact of Nanoscale Morphology on Charge Carrier Delocalization and Mobility in an Organic Semiconductor

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