Molecular dynamics and charge transport in organic semiconductors: a classical approach to modeling electron transfer

Pelzer, Kenley M.; Vázquez-Mayagoitia, Álvaro; Ratcliff, Laura E.; Tretiak, Sergei; Bair, Raymond A.; Gray, Stephen K.; Voorhis, Troy Van; Larsen, Ross E.; Darling, Seth B.

doi:10.1039/c6sc04547b

Cited by 14 publications

(7 citation statements)

References 79 publications

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“…The PBE functional (Perdew et al, 1996) was used for transfer integral calculations for computational efficiency (Baumeier et al, 2010). We previously showed (Pal et al, 2017) that this approach results in electron transfer rate for C60 in good agreement with available experimental and computational data reported elsewhere (Günes et al, 2007;Grzegorczyk et al, 2010;Ferguson et al, 2011;Nardes et al, 2012Nardes et al, , 2014Arntsen et al, 2013;Pelzer et al, 2017).…”

Section: Methodssupporting

confidence: 70%

Effect of Nuclear Motion on Charge Transport in Fullerenes: A Combined Density Functional Tight Binding—Density Functional Theory Investigation

et al. 2019

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Fullerene-based materials are widely used as acceptor and electron transport layer materials in organic and planar perovskite solar cells. Modeling of electronic properties such as band alignment and charge transport for these applications is typically done using optimized geometries. Here, we estimate the effects of nuclear motions on band structure, and electron and hole transport in two prototypical fullerenes, C60 and C70. We model the dynamics in solid fullerenes using Density Functional Tight Binding and we use the Density Functional Theory based Projection of Monomer Orbitals on Dimer Orbitals (DIPRO) approach to estimate the effects on the charge transfer integral in the Marcus approximation. We show that room-temperature molecular dynamics cause a shift and spread of frontier orbital energies on the order of 0.1 eV, which leads to an increase by more than a factor of two in the Marcus exponent, and can cause a decrease by up to orders of magnitude in the overlap integral, leading, in most cases, to an overall decrease in the charge transport rate.

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Section: Methodssupporting

confidence: 70%

Effect of Nuclear Motion on Charge Transport in Fullerenes: A Combined Density Functional Tight Binding—Density Functional Theory Investigation

et al. 2019

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“…where k =charge transfer rate, V c =direct effective electron coupling, and λ =reorganization energy of the system, see the Supporting Information for more details . By applying the Einstein relation ( μ = eD / k B T , D = kL 2 /2, where μ =mobility of charge transfer carriers, D= diffusion constant, L =mean length of particle movement) and assuming an equal number of charge carriers in different packing motifs, we estimated the conductivity value ratio as a ratio of the corresponding k values.…”

Section: Methodsmentioning

confidence: 99%

Stack the Bowls: Tailoring the Electronic Structure of Corannulene‐Integrated Crystalline Materials

et al. 2018

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We report the first examples of purely organic donor–acceptor materials with integrated π‐bowls (πBs) that combine not only crystallinity and high surface areas but also exhibit tunable electronic properties, resulting in a four‐orders‐of‐magnitude conductivity enhancement in comparison with the parent framework. In addition to the first report of alkyne–azide cycloaddition utilized for corannulene immobilization in the solid state, we also probed the charge transfer rate within the Marcus theory as a function of mutual πB orientation for the first time, as well as shed light on the density of states near the Fermi edge. These studies could foreshadow new avenues for πB utilization for the development of optoelectronic devices or a route for highly efficient porous electrodes.

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“…where k = charge transfer rate, V c = direct effective electron coupling,and l = reorganization energy of the system, see the Supporting Information for more details. [44,45] By applying the Einstein relation (m = eD/k B T, D = kL 2 /2, where m = mobility of charge transfer carriers, D = diffusion constant, L = mean length of particle movement) and assuming an equal number of charge carriers in different packing motifs,w ee stimated the conductivity value ratio as aratio of the corresponding k values.W ithin this model, we found that as hift from noncolumnar organization to aone-dimensional corannulene stack could result in ac irca 42-fold increase in conductivity values (see the Supporting Information for adetailed description). Therefore,t he experimentally observed conductivity enhancement could be attributed not only to the pB integration and/or D-A corannulene-host communication Figure 4.…”

Section: Angewandte Chemiementioning

confidence: 99%

Stack the Bowls: Tailoring the Electronic Structure of Corannulene‐Integrated Crystalline Materials

et al. 2018

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We report the first examples of purely organic donor-acceptor materials with integrated π-bowls (πBs) that combine not only crystallinity and high surface areas but also exhibit tunable electronic properties, resulting in a four-orders-of-magnitude conductivity enhancement in comparison with the parent framework. In addition to the first report of alkyne-azide cycloaddition utilized for corannulene immobilization in the solid state, we also probed the charge transfer rate within the Marcus theory as a function of mutual πB orientation for the first time, as well as shed light on the density of states near the Fermi edge. These studies could foreshadow new avenues for πB utilization for the development of optoelectronic devices or a route for highly efficient porous electrodes.

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Molecular dynamics and charge transport in organic semiconductors: a classical approach to modeling electron transfer

Abstract: Using ab initio calculations of charges in PCBM fullerenes, a multiscale approach applies classical molecular dynamics to model charge transfer.

Cited by 14 publications

References 79 publications

Effect of Nuclear Motion on Charge Transport in Fullerenes: A Combined Density Functional Tight Binding—Density Functional Theory Investigation

Effect of Nuclear Motion on Charge Transport in Fullerenes: A Combined Density Functional Tight Binding—Density Functional Theory Investigation

Stack the Bowls: Tailoring the Electronic Structure of Corannulene‐Integrated Crystalline Materials

Stack the Bowls: Tailoring the Electronic Structure of Corannulene‐Integrated Crystalline Materials

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