Singlet fission (SF) has the potential to supersede the traditional solar energy conversion scheme by means of boosting the photonto-current conversion efficiencies beyond the 30% ShockleyQueisser limit. Here, we show unambiguous and compelling evidence for unprecedented intramolecular SF within regioisomeric pentacene dimers in room-temperature solutions, with observed triplet quantum yields reaching as high as 156 ± 5%. Whereas previous studies have shown that the collision of a photoexcited chromophore with a ground-state chromophore can give rise to SF, here we demonstrate that the proximity and sufficient coupling through bond or space in pentacene dimers is enough to induce intramolecular SF where two triplets are generated on one molecule.acene oligomers | excited states | singlet fission | multireference perturbation theory | time-resolved spectroscopy S inglet fission (SF) is a spin-allowed process to convert one singlet excited state into two triplet excited states, namely a correlated triplet pair (1). The ability to effectively implement SF processes in solar cells could allow for more efficient harvesting of high-energy photons from the solar spectrum and allow for the design of solar cells to circumvent the Shockley-Queisser performance limit (2). Indeed, several recent studies have demonstrated remarkably efficient solar cell devices based on SF (3-6).One requirement that needs to be met to achieve SF is that the photoexcited chromophore in its singlet excited state must share its energy with a neighboring ground-state chromophore. As such, the potential of coupled chromophores to afford two triplet excited states via SF has been elucidated in, for example, a tetracene dimer with an SF yield of around 3% (3, 7). Additionally, past experiments in single-crystal, polycrystalline, and amorphous solids of pentacene have documented that the efficiency of SF relates to the electronic coupling between these two chromophores (8, 9). Hence, molecular ordering in terms of crystal packing, that is, proximity, distances, orbital overlap, etc., is decisive with respect to gaining full control over and to finetuning interchromophoric interactions in the solid state (10, 11). Of equal importance are the thermodynamic requirements, namely that the energy of the lowest-lying singlet absorbing state must match or exceed the energy of two triplet excited states (S 1 ≥ 2T 1 ) (11). In light of both aspects, hydrocarbons such as acenes--tetracene, pentacene, hexacene--and their derivatives are at the forefront of investigations toward a sound understanding and development of molecular building blocks for SF. In tetracenes, the singlet-and triplet-pair energy levels are nearly degenerate (S 1 = 2T 1 ), leaving no or little standard enthalpy of reaction for SF (12). In solution, the latter is, however, offset by sizable entropy rendering the process rather slow and, thus, inefficient (13). In addition, the low SF yield relates to the dimer geometry. Its nature hinders electronic coupling through space, leaving only thro...
When molecular dimers, crystalline films or molecular aggregates absorb a photon to produce a singlet exciton, spin-allowed singlet fission may produce two triplet excitons that can be used to generate two electron–hole pairs, leading to a predicted ∼50% enhancement in maximum solar cell performance. The singlet fission mechanism is still not well understood. Here we report on the use of time-resolved optical and electron paramagnetic resonance spectroscopy to probe singlet fission in a pentacene dimer linked by a non-conjugated spacer. We observe the key intermediates in the singlet fission process, including the formation and decay of a quintet state that precedes formation of the pentacene triplet excitons. Using these combined data, we develop a single kinetic model that describes the data over seven temporal orders of magnitude both at room and cryogenic temperatures.
A new theory is proposed to accurately simulate quantum dynamics in systems of identical particles. It is based on the second quantization formalism of many-body quantum theory, in which the Fock space is represented by occupation-number states. Within this representation the overall Fock space can be formally decomposed into smaller subspaces, and the wave function can be expressed as a multilayer multiconfiguration Hartree expansion involving subvectors in these subspaces. The theory unifies the multilayer multiconfiguration time-dependent Hartree theory for both distinguishable and indistinguishable particles. Specific formulations are given for systems of identical fermions, bosons, and combinations thereof. Practical implementations are discussed, especially for the case of fermions, to include the operator algebra that enforces the symmetry of identical particles. The theory is illustrated by a numerical example on vibrationally coupled electron transport.
Silicon-based solar cells are approaching the thermodynamic limit of efficiency (Shockley-Queisser limit). Simultaneously, fossil fuels are strongly linked to climate changes. Consequently, new approaches are necessary to satisfy the world's steadily increasing energy demand. Singlet fission (SF) is a process overcoming the core assumptions that Shockley and Queisser postulated for their calculations: it is predicted to generate two charges per photon rather than only one! Basel et al. provide evidence for a charge-transfer-mediated mechanism of SF in a nonconjugated, rigid pentacene dimer.
aWe show unambiguous and compelling evidence by means of pump-probe experiments, which are complemented by calculations using ab initio multireference perturbation theory, for intramolecular singlet fission (SF) within two synthetically tailored pentacene dimers with cross-conjugation, namely XC1 and XC2. The two pentacene dimers differ in terms of electronic interactions as evidenced by perturbation of the ground state absorption spectra stemming from stronger through-bond contributions in XC1 as confirmed by theory. Multiwavelength analysis, on one hand, and global analysis, on the other hand, confirm that the rapid singlet excited state decay and triplet excited state growth relate to SF. SF rate constants and quantum yields increase with solvent polarity. For example, XC2 reveals triplet quantum yields and rate constants as high as 162 ± 10% and (0.7 ± 0.1) × 10 12 s −1, respectively, in room temperature solutions.
Photoinduced electron transfer processes in dye−semiconductor systems are studied employing a recently proposed method based on a model Hamiltonian where the parameters are determined by first-principles electronic structure calculations. The systems investigated include the molecules pyridine and perylene, which are anchored via phosphonic or carboxylic acid groups to a titanium dioxide nanocluster. The dynamics of the electron injection process is analyzed in some detail. Furthermore, the applicability of different rate theories to characterize the electron transfer dynamics is discussed.
A theoretical study of photoinduced heterogeneous electron transfer in the dye-semiconductor system coumarin 343-TiO(2) is presented. The study is based on a generic model for heterogeneous electron transfer reactions, which takes into account the coupling of the electronic states to the nuclear degrees of freedom of coumarin 343 as well as to the surrounding solvent. The quantum dynamics of the electron injection process is simulated employing the recently proposed multilayer formulation of the multiconfiguration time-dependent Hartree method. The results reveal an ultrafast injection dynamics of the electron from the photoexcited donor state into the conduction band of the semiconductor. Furthermore, the mutual influence of electronic injection dynamics and nuclear motion is analyzed in some detail. The analysis shows that--depending on the time scale of nuclear motion--electronic vibrational coupling can result in electron transfer driven by coherent vibrational motion or vibrational motion induced by ultrafast electron transfer.
Two approaches to describe the thermodynamics of a subsystem that interacts with a thermal bath are considered. Within the first approach, the mean system energy E S is identified with the expectation value of the system Hamiltonian, which is evaluated with respect to the overall (system+bath) equilibrium distribution. Within the second approach, the system partition function Z S is considered as the fundamental quantity, which is postulated to be the ratio of the overall (system+bath) and the bath partition functions, and the standard thermodynamic relation E S = −d(ln Z S )/dβ is used to obtain the mean system energy. Employing both classical and quantum mechanical treatments, the advantages and shortcomings of the two approaches are analyzed in detail for various different systems. It is shown that already within classical mechanics both approaches predict significantly different results for thermodynamic quantities provided the system-bath interaction is not bilinear or the system of interest consists of more than a single particle. Based on the results, it is concluded that the first approach is superior.
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