The ultrafast formation of charge transfer excitons (CTXs) in regioregular poly(3-hexyl thiophene) (rrP3HT) domains is elucidated by electronic structure and quantum dynamical studies of an aggregate model system comprising five stacked quaterthiophene units. Using a multistate vibronic coupling Hamiltonian parametrized by TDDFT calculations for 13 electronic states of Frenkel and CTX type, along with 78 vibrational modes, quantum dynamical simulations are carried out using the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method. In line with time-resolved spectroscopic results et al. Nat. Commun. 2016, 7, 13742], it is found that CTX formation occurs immediately upon photoexcitation, accompanied by sustained regular oscillations with a ∼22 fs periodicity. These coherent features, whose presence may seem surprising in a high-dimensional aggregate or thin film material, can be traced back to a dominant vibronic signature of CC stretch-type high-frequency modes. These vibrational signatures are found to be enhanced due to a collective vibronic response that is prompted by the initial generation of a delocalized bright exciton and its subsequent relaxation, by internal conversion, to a polaronic local exciton ground state.

Conjugated donor-acceptor block co-oligomers that self-organize into D-A mesomorphic arrays have raised increasing interest due to their potential applications in organic solar cells. We report here a combined experimental and computational study of charge transfer (CT) state formation and recombination in isolated donor-spacer-acceptor oligomers based on bisthiophene-fluorene (D) and perylene diimide (A), which have recently shown to self-organize to give a mesomorphic lamellar structure at room temperature. Using femtosecond transient absorption spectroscopy and Time-Dependent Density Functional Theory in combination with the Marcus-Jortner formalism, the observed increase of the CT lifetimes is rationalized in terms of a reduced electronic coupling between D and A brought about by the chemical design of the donor moiety. A marked dependence of the CT lifetime on solvent polarity is observed, underscoring the importance of electrostatic effects and those of the environment at large. The present investigation therefore calls for a more comprehensive design approach including the effects of molecular packing.

We review recent work employing high-dimensional quantum dynamical techniques to study ultrafast charge separation in functional organic materials, in view of understanding the key microscopic factors that lead to efficient charge generation in photovoltaics applications. As highlighted by recent experiments, these processes can be guided by quantum coherence, despite the presence of static and dynamic disorder. The present approach combines first-principles parametrized lattice Hamiltonians, based on Time-Dependent Density Functional Theory (TDDFT) and/or high-level electronic structure calculations, with accurate quantum dynamics simulations using the Multi-Configuration Time-Dependent Hartree (MCTDH) method. This contribution specifically addresses the mechanism of charge generation in (i) regioregular oligothiophene-fullerene aggregates, and (ii) highly ordered oligothiophene-perylene diimide co-oligomer assemblies. These studies highlight that chemical design of donor-acceptor combinations needs to account for the effects of electronic delocalization and the modified energetics due to molecular packing, as well as multiple transfer pathways and internal conversion channels induced by vibronic interactions.excitonic states, molecular packing, organic photovoltaics, quantum dynamics, ultrafast charge separation | I N TR ODU C TI ONIn organic donor-acceptor (DA) materials developed for photovoltaics applications, the break-up of photogenerated excitons at DA heterojunction interfaces initiates the irreversible separation of charge carriers. [1,2] Over the past few years, it has become increasingly clear that the efficiency of this process depends on a complex interplay of different factors, such that design principles based on the engineering of molecular structure and DA band offsets are not necessarily sufficient. Indeed, the photochemical processes inherent to the molecular donor and acceptor materials necessitate a molecular-level analysis that may deviate from the basic picture derived from semiconductor physics. This is underscored by an increasing body of evidence from time-resolved spectroscopies [3][4][5][6][7] showing that the elementary energy and charge transfer (CT) processes in typical photovoltaic materials are often of quantum coherent character. Conventional kinetic descriptions are therefore not apt to render a faithful picture of these elementary steps, and may only be valid on longer time scales where hopping type transport dynamics sets in.Even long-range electron-hole separation under the effect of a Coulomb barrier may not necessarily obey the slow, thermally activated dynamics described by the Onsager-Braun model. [8] Indeed, recent time-resolved experiments, for example, for prototypical blends of poly-3-hexylthiophene (P3HT) and the fullerene derivative [6,6]-phenyl-C 61 butyric acid methyl ester (PCBM) and related systems, report ultrafast longrange charge separation, especially in materials exhibiting regioregular morphologies. [9][10][11][12][13][14][15] To explain these ob...

This study addresses the mechanism of ultrafast charge separation in regioregular oligothiophene-fullerene assemblies representative of poly-3-hexylthiophene (P3HT)-[6,6]-phenyl-C61 butyric acid methyl ester (PCBM) heterojunctions, with special emphasis on the inclusion of charge transfer excitons in the oligothiophene phase. The formation of polaronic inter-chain charge separated species in highly ordered oligothiophene has been demonstrated in recent experiments and could have a significant impact on the net charge transfer to the fullerene acceptor. The present approach combines a first-principles parametrized multi-site Hamiltonian, based on time-dependent density functional theory calculations, with accurate quantum dynamics simulations using the multi-layer multi-configuration time-dependent Hartree method. Quantum dynamical studies are carried out for up to 182 electronic states and 112 phonon modes. The present analysis follows up on our previous study of (Huix-Rotllant et al 2015 J. Phys. Chem. Lett. 6 1702) and significantly expands the scope of this analysis by including the dynamical role of charge transfer excitons. Our investigation highlights the pronounced mixing of photogenerated Frenkel excitons with charge transfer excitons in the oligothiophene domain, and the opening of new transfer channels due the creation of such charge-separated species. As a result, it turns out that the interfacial donor/acceptor charge transfer state can be largely circumvented due to the presence of charge transfer excitons. However, the latter states in turn act as a trap, such that the free carrier yield observed on ultrafast time scales is tangibly reduced. The present analysis underscores the complexity of the transfer pathways at P3HT-PCBM type junctions.

Vibronic coupling models for donor-acceptor aggregates using an effective-mode scheme: Application to mixed Frenkel and charge-transfer excitons in oligothiophene aggregates.

Combined electronic structure and quantum dynamical calculations are employed to investigate charge separation in a novel class of covalently bound bisthiophene-perylene diimide type donor-acceptor (DA) co-oligomer aggregates. In an earlier spectroscopic study of this DA system in a smectic liquid crystalline (LC) film, efficient and ultrafast (subpicosecond) initial charge separation was found to be followed by rapid recombination. By comparison, the same DA system in solution exhibits ultrafast resonant energy transfer followed by slower (picosecond scale) charge separation. The present first-principles study explains these contrasting observations, highlighting the role of an efficient intermolecular charge-transfer pathway that results from the molecular packing in the LC phase. Despite the efficiency of this primary charge-transfer step, long-range charge separation is impeded by a comparatively high Coulomb barrier in conjunction with small electron- and hole-transfer integrals. Quantum dynamical calculations are carried out for a fragment-based model Hamiltonian, parametrized by ab initio second-order Algebraic Diagrammatic Construction (ADC(2)) and Time-Dependent Density Functional Theory (TDDFT) electronic structure calculations. Simulations of coherent vibronic quantum dynamics for up to 156 electronic states and 48 modes are performed using the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method. Excellent agreement with experimentally determined charge separation time scales is obtained, and the spatially coherent nature of the dynamics is analyzed.

Nitrodibenzofuran (NDBF) has recently been established as photolabile protecting group and efficiently used as two-photon active cage. In this work, a computational approach is exploited to rationally design improved two-photon active caging groups based on this NDBF chromophore. For this objective, first the two-photon absorption (TPA) properties of NDBF are investigated in detail and a suitable theoretical approach for the reliable simulation of TPA spectra of this class of compounds is identified. Then, virtual chemical modifications are performed by introduction of substituents at the chromophore and replacement of the central furan ring by pyrolle, thiophene, and borrole heterocycles. Subsequently, the TPA properties of the resulting compounds are computed, and the influences of the chemical modifications on TPA properties investigated in detail. The most promising candidates with largely increased two-photon uncaging efficiencies are dimethylamino-substituted derivatives of NDBF, nitrodibenzopyrrol, and nitrodibenzothiophene.

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