Exciton dissociation at donor-acceptor heterojunctions: Dynamics using the collective effective mode representation of the spin-boson model

Chenel, Aurélie; Mangaud, Etienne; Burghardt, Irène; Meier, Christoph; Desouter-Lecomte, Michèle

doi:10.1063/1.4861853

Cited by 24 publications

(41 citation statements)

References 52 publications

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“…7), the vibronic model evolves from an inverse Marcus donor-acceptor shape for R = 2.5 and 3 Å to a normal Marcus profile for R = 3.5 Å [52]. This agrees with the behavior of the population evolution seen in Fig.…”

Section: Effective Modesupporting

confidence: 77%

“…However, it is not sufficient to build a vibronic one-dimensional model that requires the displacement of the oscillators. Hence in the next section, we compare these findings with results obtained from the effective mode theory already used in a previous paper [52]. …”

Section: Signature Of the Bath Dynamicsmentioning

confidence: 75%

“…However, it is not the case for the Ohmic one where the integral giving X 1 diverges and a cutoff frequency is required [52].…”

Section: Effective Modementioning

confidence: 99%

“…The collective mode, often called 'effective mode' can still be coupled to a secondary bath. Different definitions of a collective mode have been proposed [49,50,52,72,73]. We have chosen here the direction which endorses all the vibronic couplings, i.e.…”

Section: Effective Modementioning

confidence: 99%

“…Electronic dynamics has first been treated by the MCTDH (Multi Configuration Time Dependent Hartree) method with an approximate model Hamiltonian [47][48][49][50]55,56] by sampling the oscillator bath formed by all the normal modes of both fragments. Then dissipative dynamics has been carried out by HEOM with a hierarchical decomposition of the spectral density [51] or by the auxiliary matrix method in a perturbative treatment of the vibronic model obtained by including one effective bath mode in the system Hamiltonien [52]. The vibronic hot nature of the charge transfer has also been considered in a multi-state model [53].…”

Section: Introductionmentioning

confidence: 99%

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Analysis of the non-Markovianity for electron transfer reactions in an oligothiophene-fullerene heterojunction

2017

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a b s t r a c tThe non-Markovianity of the electron transfer in an oligothiophene-fullerene heterojunction described by a spin-boson model is analyzed using the time dependent decoherence canonical rates and the volume of accessible states in the Bloch sphere. The dynamical map of the reduced electronic system is computed by the hierarchical equations of motion methodology (HEOM) providing an exact dynamics. Transitory witness of non-Markovianity is linked to the bath dynamics analyzed from the HEOM auxiliary matrices. The signature of the collective bath mode detected from HEOM in each electronic state is compared with predictions of the effective mode extracted from the spectral density. We show that including this main reaction coordinate in a one-dimensional vibronic system coupled to a residual bath satisfactorily describes the electron transfer by a simple Markovian Redfield equation. Non-Markovianity is computed for three inter fragment distances and compared with a priori criterion based on the system and bath characteristic timescales.

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Section: Effective Modesupporting

confidence: 77%

Section: Signature Of the Bath Dynamicsmentioning

confidence: 75%

“…However, it is not the case for the Ohmic one where the integral giving X 1 diverges and a cutoff frequency is required [52].…”

Section: Effective Modementioning

confidence: 99%

Section: Effective Modementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Analysis of the non-Markovianity for electron transfer reactions in an oligothiophene-fullerene heterojunction

2017

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Non-Markovian reduced dynamics of ultrafast charge transfer at an oligothiophene–fullerene heterojunction

et al. 2014

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We extend our recent quantum dynamical study of the exciton dissociation and charge transfer at an oligothiophene-fullerene heterojunction interface (H. Tamura, R. Martinazzo, M. Ruckenbauer, and I. Burghardt, J. Chem. Phys. 137 (2012) 22A540) by investigating the process using the non-perturbative hierarchical equations of motion (HEOM) approach. Based upon an effective mode reconstruction of the spectral density the effect of temperature on the charge transfer is studied using reduced density matrices. It was found that the temperature had little effect on the charge transfer and a coherent dynamics persists over the first few tens of femtoseconds, indicating that the primary charge transfer step proceeds by an activationless pathway.

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Ultrafast Nonadiabatic Dynamics of Singlet Fission: Quantum Dynamics with the Multilayer Multiconfigurational Time-Dependent Hartree (ML-MCTDH) Method

et al. 2016

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Singlet fission (SF) is supposed to potentially improve the efficiency of solar energy conversion in organic photovoltaic systems. The multilayer multiconfigurational time-dependent Hartree (ML-MCTDH) method was employed to describe the singlet fission of the pentacene system with a three-state model. The ML-MCTDH result agrees well with the previous simulations using the Redfield theory, the hierarchical equation of motion (HEOM) and the symmetrical quasi-classical (SQC) theory. We carefully investigated the role of vibrational modes with different frequencies in singlet fission dynamics. Interestingly, we observed the important contribution of a few modes with frequency resonance to electronic transition. Such a finding can be understood by revisiting the superexchange mechanism within the framework of Fermi’s golden rule. As a numerically exact method, ML-MCTDH not only provides an accurate description of the microscopy insight of the SF dynamics but also provides benchmark results to examine the performance of other approximated dynamical methods.

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Exciton dissociation at donor-acceptor heterojunctions: Dynamics using the collective effective mode representation of the spin-boson model

Cited by 24 publications

References 52 publications

Analysis of the non-Markovianity for electron transfer reactions in an oligothiophene-fullerene heterojunction

Analysis of the non-Markovianity for electron transfer reactions in an oligothiophene-fullerene heterojunction

Non-Markovian reduced dynamics of ultrafast charge transfer at an oligothiophene–fullerene heterojunction

Ultrafast Nonadiabatic Dynamics of Singlet Fission: Quantum Dynamics with the Multilayer Multiconfigurational Time-Dependent Hartree (ML-MCTDH) Method

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