Exciton/Charge-Transfer Electronic Couplings in Organic Semiconductors

Difley, Seth; Voorhis, Troy Van

doi:10.1021/ct100508y

Cited by 66 publications

(67 citation statements)

References 56 publications

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“…A more sophisticated yet still approximate alternative, which would require an extension of the current FDE-ET formalism, is to construct approximate excited-state wavefunctions on the basis of TDDFT results, as employed in Ref. 62.…”

Section: Spin States Of the Diabatic Wavefunctions And Coupling Tomentioning

confidence: 99%

Describing long-range charge-separation processes with subsystem density-functional theory

Solovyeva

Pavanello

Neugebauer

2014

The Journal of Chemical Physics

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Long-range charge-transfer processes in extended systems are difficult to describe with quantum chemical methods. In particular, cost-effective (non-hybrid) approximations within time-dependent density functional theory (DFT) are not applicable unless special precautions are taken. Here, we show that the efficient subsystem DFT can be employed as a constrained DFT variant to describe the energetics of long-range charge-separation processes. A formal analysis of the energy components in subsystem DFT for such excitation energies is presented, which demonstrates that both the distance dependence and the long-range limit are correctly described. In addition, electronic couplings for these processes as needed for rate constants in Marcus theory can be obtained from this method. It is shown that the electronic structure of charge-separated states constructed by a positively charged subsystem interacting with a negatively charged one is difficult to converge - charge leaking from the negative subsystem to the positive one can occur. This problem is related to the delocalization error in DFT and can be overcome with asymptotically correct exchange-correlation (XC) potentials or XC potentials including a sufficiently large amount of exact exchange. We also outline an approximate way to obtain charge-transfer couplings between locally excited and charge-separated states.

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Section: Spin States Of the Diabatic Wavefunctions And Coupling Tomentioning

confidence: 99%

Describing long-range charge-separation processes with subsystem density-functional theory

Solovyeva

Pavanello

Neugebauer

2014

The Journal of Chemical Physics

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“…Approximate CT wave functions have previously been constructed using, e.g., constrained DFT to study their coupling to localized excitations derived from TDDFT. 27 GW -BSE allows to derive both from the same Hamiltonian, and to this end, intermolecular CT excitations of types A – B + and A + B – are constructed within GW -BSE-DIPRO as product states from the respective monomer single-particle orbitals. All the couplings between the CT excitations, as well as to the localized monomer excitons, are calculated.…”

Section: Introductionmentioning

confidence: 99%

Intermolecular Singlet and Triplet Exciton Transfer Integrals from Many-Body Green’s Functions Theory

Wehner

Baumeier

2017

J. Chem. Theory Comput.

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A general approach to determine orientation and distance-dependent effective intermolecular exciton transfer integrals from many-body Green’s functions theory is presented. On the basis of the GW approximation and the Bethe–Salpeter equation (BSE), a projection technique is employed to obtain the excitonic coupling by forming the expectation value of a supramolecular BSE Hamiltonian with electron–hole wave functions for excitations localized on two separated chromophores. Within this approach, accounting for the effects of coupling mediated by intermolecular charge transfer (CT) excitations is possible via perturbation theory or a reduction technique. Application to model configurations of pyrene dimers shows an accurate description of short-range exchange and long-range Coulomb interactions for the coupling of singlet and triplet excitons. Computational parameters, such as the choice of the exchange-correlation functional in the density-functional theory (DFT) calculations that underly the GW-BSE steps and the convergence with the number of included CT excitations, are scrutinized. Finally, an optimal strategy is derived for simulations of full large-scale morphologies by benchmarking various approximations using pairs of dicyanovinyl end-capped oligothiophenes (DCV5T), which are used as donor material in state-of-the-art organic solar cells.

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“…For example, this method has been used to calculate charge transfer rates via Marcus theory. 29,37–42 In 2000, Kim et al suggested that a charge could be treated via the Langevin equation. 43 Beyond CDFT and LMD, many other models of charge transport in organic semiconductors have been proposed (see ref.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2017

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Exciton/Charge-Transfer Electronic Couplings in Organic Semiconductors

Cited by 66 publications

References 56 publications

Describing long-range charge-separation processes with subsystem density-functional theory

Describing long-range charge-separation processes with subsystem density-functional theory

Intermolecular Singlet and Triplet Exciton Transfer Integrals from Many-Body Green’s Functions Theory

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

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