Singlet fission is an excitation multiplication process in molecular systems that can circumvent energy losses and significantly boost solar cell efficiencies; however, the nature of a critical intermediate that enables singlet fission and details of its evolution into multiple product excitations remain obscure. We resolve the initial sequence of events comprising the fission of a singlet exciton in solids of pentacene derivatives using femtosecond transient absorption spectroscopy. We propose a three-step model of singlet fission that includes two triplet-pair intermediates and show how transient spectroscopy can distinguish initially interacting triplet pairs from those that are spatially separated and noninteracting. We find that the interconversion of these two triplet-pair intermediates is limited by the rate of triplet transfer. These results clearly highlight the classical kinetic model of singlet fission and expose subtle details that promise to aid in resolving problems associated with triplet extraction.

The intramolecular charge-transfer (CT) dynamics of a rigid and strongly conjugated perylenediimide-bridge-perylene dyad (PDIPe) has been investigated in dichloromethane using ultrafast transient electronic absorption spectroscopy and quantum chemical calculations. The strong electronic coupling between the dyad units gives rise to a CT band. Its photoexcitation forms a delocalized CT state with well-preserved ion bands despite the strong coupling. In the dyad, the electronic transition dipole moment of the electron donor perylene is aligned along the axis of the electric field vector with respect to the CT species. This alignment makes the donor sensitive to the Stark effect and thus charge density fluctuations in the CT state. Charge localization on the picosecond time scale manifests as a time-dependent Stark shift in the visible region. Quantum chemical calculations reveal a twist around the acetylene bridging unit to be the responsible mechanism generating a partial to an almost complete CT state. An estimate of the electric field strength in the CT state yields approximately 25 MV/cm, which increases to around 31 MV/cm during charge localization. Furthermore, the calculations illustrate the complexity of electronic structure in this strongly delocalized superchromophore and reflect the complications in the interpretation of transient absorption results when compared to steady-state approaches such as spectroelectrochemistry and model chromophore experiments such as photoinduced bimolecular charge transfer.

•Dephasing time of vibrational coherences through Inverse Fourier filtering analysis.•Coherence along reactive modes dephase prior to back-electron transfer process.•Small Franck-Condon factors of resonant quanta reduces effective coupling.•Energy gap fluctuations by solvation dynamics eliminate coherent contributions.•Back-electron transfer process is predominantly incoherent.The possible role of coherent vibrational motion in ultrafast photo-induced electron transfer remains unclear despite considerable experimental and theoretical advances. We revisited this problem by tracking the back-electron transfer (bET) process in Betaine-30 with broadband pump-probe spectroscopy. Dephasing time constant of certain high-frequency vibrations as a function of solvent shows a trend similar to the ET rates. In the purview of Bixon-Jortner model, high-frequency quantum vibrations bridge the reactant-product energy gap by providing activationless vibronic channels. Such interaction reduces the effective coupling significantly and thereby the coherence effects are eliminated due to energy gap fluctuations, making the back-electron transfer incoherent.Download high-res image (153KB)Download full-size image

In this article we study the ultrafast dynamics of excitons and charge carriers photogenerated in two-dimensional in-plane heterostructures, namely, CdSe–CdTe nanoplatelets. We combine transient absorption and two-dimensional electronic spectroscopy to study charge transfer and delocalization from a few tens of femtoseconds to several nanoseconds. In contrast with spherical nanocrystals, the relative alignment of the electron and hole states of CdSe and CdTe in thin 2D nanoplatelets does not lead to a type-II heterostructure. Following the excitation in CdSe or CdTe materials, the electron preferentially delocalises instantaneously over the whole heterostructure. In addition, depending on the crown material (CdTe versus CdTeSe), the hole transfers either to trap states or to the crown, within a few hundreds of femtoseconds. We conclude that the photoluminescence band, at lower energy than the CdSe and CdTe first exciton transition, does not result from the recombination of the charge carriers at the charge transfer state but involves localised hole states.

Quantitative singlet fission has been observed for a variety of acene derivatives such as tetracene and pentacene, and efforts to extend the library of singlet fission compounds is of current interest. Preliminary calculations suggest anthradithiophenes exhibit significant exothermicity between the first optically-allowed singlet state, S1, and 2 × T1 with an energy difference of >5000 cm−1. Given the fulfillment of this ingredient for singlet fission, here we investigate the singlet fission capability of a difluorinated anthradithiophene dimer (2ADT) covalently linked by a (dimethylsilyl)ethane bridge and derivatized by triisobutylsilylethynyl (TIBS) groups. Photophysical characterization of 2ADT and the single functionalized ADT monomer were carried out in toluene and acetone solution via absorption and fluorescence spectroscopy, and their photo-initiated dynamics were investigated with time-resolved fluorescence (TRF) and transient absorption (TA) spectroscopy. In accordance with computational predictions, two conformers of 2ADT were observed via fluorescence spectroscopy and were assigned to structures with the ADT cores trans or cis to one another about the covalent bridge. The two conformers exhibited markedly different excited state deactivation mechanisms, with the minor trans population being representative of the ADT monomer showing primarily radiative decay, while the dominant cis population underwent relaxation into an excimer geometry before internally converting to the ground state. The excimer formation kinetics were found to be solvent dependent, yielding time constants of ∼1.75 ns in toluene, and ∼600 ps in acetone. While the difference in rates elicits a role for the solvent in stabilizing the excimer structure, the rate is still decidedly long compared to most singlet fission rates of analogous dimers, suggesting that the excimer is neither a kinetic nor a thermodynamic trap, yet singlet fission was still not observed. The result highlights the sensitivity of the electronic coupling element between the singlet and correlated triplet pair states, to the dimer conformation in dictating singlet fission efficiency even when the energetic requirements are met.

The process of photosynthesis is initiated by the capture of sunlight by a network of light-absorbing molecules (chromophores), which are also responsible for the subsequent funneling of the excitation energy to the reaction centers. Through evolution, genetic drift, and speciation, photosynthetic organisms have discovered many solutions for light harvesting. In this review, we describe the underlying photophysical principles by which this energy is absorbed, as well as the mechanisms of electronic excitation energy transfer (EET). First, optical properties of the individual pigment chromophores present in light-harvesting antenna complexes are introduced, and then we examine the collective behavior of pigment−pigment and pigment−protein interactions. The description of energy transfer, in particular multichromophoric antenna structures, is shown to vary depending on the spatial and energetic landscape, which dictates the relative coupling strength between constituent pigment molecules. In the latter half of the article, we focus on the light-harvesting complexes of purple bacteria as a model to illustrate the present understanding of the synergetic effects leading to EET optimization of light-harvesting antenna systems while exploring the structure and function of the integral chromophores. We end this review with a brief overview of the energy-transfer dynamics and pathways in the light-harvesting antennas of various photosynthetic organisms.

Amorphous nanoparticles of the singlet fission chromophore 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-Pn) are fully crystallized through co-precipitation with a chemical additive. Time-resolved measurements indicate that singlet fission in the crystalline nanoparticles is quantitative, or lossless, whereas losses are evident in the amorphous nanoparticles as a result of frustrated triplet pair separation. Because triplet pairs form rapidly and separate slowly in amorphous material, mixed-phase samples are unable to compensate for these losses.

In this work, we characterize the energy and electron transfer kinetics of a zinc phthalocyanine–perylenediimide dyad (ZnPc–PDI) in various solvents using steady-state and tunable narrowband pump–probe spectroscopy. We fit the ultrafast data with global analysis techniques and find that upon excitation of the PDI moiety (pump pulse at 540 nm), the excitation energy transfer (EET) rate to the ZnPc moiety displays a solvent sensitivity that we attribute to changes in the relative equilibrium moiety orientation. We rationalize these observations by considering the nature of the non-rigid bridge used to link the two moieties as well as the degenerate nature of the Q band transitions in the ZnPc species. By tuning the pulse into resonance with the ZnPc Q band (685 nm) we can directly photo-induce an electron transfer (ET) process back to the PDI moiety. Employing the same global analysis, we find that the dynamics of the ultrafast electron transfer are completely kinetically controlled according to the Bixon-Jortner model of barrierless solvent-controlled curve crossing, while the recombination to reform the ground state is well-described using the static energetic picture according to Marcus theory.

Conjugated polymers are complex multichromophore systems, with emission properties strongly dependent on the electronic energy transfer through active subunits. Although the packing of the conjugated chains in the solid state is known to be a key factor to tailor the electronic energy transfer and the resulting optical properties, most of the current solution-based processing methods do not allow for effectively controlling the molecular order, thus making the full unveiling of energy transfer mechanisms very complex. Here we report on conjugated polymer fibers with tailored internal molecular order, leading to a significant enhancement of the emission quantum yield. Steady state and femtosecond time-resolved polarized spectroscopies evidence that excitation is directed toward those chromophores oriented along the fiber axis, on a typical time scale of picoseconds. These aligned and more extended chromophores, resulting from the high stretching rate and electric field applied during the fiber spinning process, lead to improved emission properties. Conjugated polymer fibers are relevant to develop optoelectronic plastic devices with enhanced and anisotropic properties.

We report the synthesis and characterization of cadmium selenide nanocrystals with electroactive ligands directly attached to the surface. The conventional surfactant-assisted synthesis yields nanocrystals with surfaces functionalized with insulating organic ligands. These insulating ligands act as a barrier for charge transport between nanocrystals. Electroactive (reducing/oxidizing) ligands like ferrocene and cobaltocene have potential for applications as photoexcited hole conductors and photoredox systems. Although ferrocene ligands anchored to the nanocrystal surface through insulating long-chain hydrocarbon spacers have previously been reported, this approach is limited because the charge transfer between nanocrystal and ferrocene is highly sensitive to their separation. We report here ferrocene directly bound to the inorganic core of the nanocrystal, and as a result the distance between the nanocrystals and the electroactive moiety is minimized.

In this work, we demonstrate the use of broad-band pump–probe spectroscopy to measure femtosecond solvation dynamics. We report studies of a rhodamine dye in methanol and cryptophyte algae light-harvesting proteins in aqueous suspension. Broad-band impulsive excitation generates a vibrational wavepacket that oscillates on the excited-state potential energy surface, destructively interfering with itself at the minimum of the surface. This destructive interference gives rise to a node at a certain probe wavelength that varies with time. This reveals the Gibbs free-energy changes of the excited-state potential energy surface, which equates to the solvation time correlation function. This method captures the inertial solvent response of water (∼40 fs) and the bimodal inertial response of methanol (∼40 and ∼150 fs) and reveals how protein-buried chromophores are sensitive to the solvent dynamics inside and outside of the protein environment.

Broadband optical pump and compressed white light continuum probe were used to measure the transient excited-state absorption, ground-state bleach, and stimulated emission signals of cresyl violet solution in methanol. Amplitude oscillations caused by wavepacket motion in the ground and excited electronic states were analyzed. It was found that vibrational coherences in the excited state persist for more than the experimental waiting time window of 6 ps, and the strongest mode had a dephasing time constant of 2.4 ps. We hypothesize the dephasing of the wavepacket in the excited state is predominantly caused by intramolecular vibrational relaxation (IVR). Slow IVR indicates weak mode–mode coupling and therefore weak anharmonicity of the potential of this vibration. Thus, the initially prepared vibrational wavepacket in the excited state is not significantly perturbed by nonadiabatic coupling to other electronic states, and hence the diabatic and adiabatic representations of the system are essentially identical within the Born–Oppenheimer approximation. The wavepacket therefore evolves with time in an almost harmonic potential, slowly dephased by IVR and the pure vibrational decoherence. The consistency in the position of node (phase change in the wavepacket) in the excited-state absorption and stimulated emission signals without undergoing any frequency shift until the wavepacket is completely dephased conforms to the absence of any reactive internal conversion.

We compare the singlet fission dynamics of five pentacene derivatives precipitated to form nanoparticles. Two nanoparticle types were distinguished by differences in their solid-state order and kinetics of triplet formation. Nanoparticles that comprise primarily weakly coupled chromophores lack the bulk structural order of the single crystal and exhibit nonexponential triplet formation kinetics (Type I), while nanoparticles that comprise primarily more strongly coupled chromophores exhibit order resembling that of the bulk crystal and triplet formation kinetics associated with the intrinsic singlet fission rates (Type II). In the highly ordered nanoparticles, singlet fission occurs most rapidly. We relate the molecular packing arrangement derived from the crystal structure of the pentacene derivatives to their singlet fission dynamics and find that slip stacking leads to rapid, subpicosecond singlet fission. We present evidence that exciton delocalization, coincident with an increased relative admixture of charge-transfer configurations in the description of the exciton wave function, facilitates rapid triplet pair formation in the case of single-step singlet fission. We extend the study to include two hexacene derivatives and find that these conclusions are generally applicable. This work highlights acene derivatives as versatile singlet fission chromophores and shows how chemical functionalization affects both solid-state order and exciton interactions and how these attributes in turn affect the rate of singlet fission.

Until recently, no analytical measure of many-body delocalization in open systems had been developed, yet such a measure enables characterization of how molecular excitons delocalize in photosynthetic light-harvesting complexes, and in turn helps us understand quantum coherent aspects of electronic energy transfer. In this paper we apply these measures to a model peripheral light-harvesting complex, LH2 from Rhodopseudomonas acidophila. We find how many chromophores collectively contribute to the “delocalization length” of an excitation within LH2 and how the coherent delocalization is distributed spatially. We also investigate to what extent this delocalization length is effective, by examining the impact of bipartite and multipartite entanglement in inter-ring energy transfer in LH2.

The first step of photosynthesis is the absorption of light by antenna complexes. Recent studies of light-harvesting complexes using two-dimensional electronic spectroscopy have revealed interesting coherent oscillations. Some contributions to those coherences are assigned to electronic coherence and therefore have implications for theories of energy transfer. To assign these femtosecond data and to gain insight into the interplay among electronic and vibrational resonances, we need detailed information on vibrations and coherences in the excited electronic state compared to the ground electronic state. Here, we used broad-band transient absorption and femtosecond stimulated Raman spectroscopies to record ground- and excited-state coherences in four related photosynthetic proteins: PC577 from Hemiselmis pacifica CCMP706, PC612 from Hemiselmis virescens CCAC 1635 B, PC630 from Chroomonas CCAC 1627 B (marine), and PC645 from Chroomonas mesostigmatica CCMP269. Two of those proteins (PC630 and PC645) have strong electronic coupling while the other two proteins (PC577 and PC612) have weak electronic coupling between the chromophores. We report vibrational spectra for the ground and excited electronic states of these complexes as well as an analysis of coherent oscillations observed in the broad-band transient absorption data.

Singlet fission to form a pair of triplet excitations on two neighboring molecules and the reverse process, triplet–triplet annihilation to upconvert excitation, have been extensively studied. Comparatively little work has sought to examine the properties of the intermediate state in both of these processes—the bimolecular pair state. Here, the eigenstates constituting the manifold of 16 bimolecular pair excitations and their relative energies in the weak-coupling regime are reported. The lowest-energy states obtained from the branching diagram method are the triplet pairs with overall singlet spin |X1⟩ ≈ 1[TT] and quintet spin |Q⟩ ≈ 5[TT]. It is shown that triplet pair states can be separated by a triplet–triplet energy-transfer mechanism to give a separated, yet entangled triplet pair 1[T···T]. Independent triplets are produced by decoherence of the separated triplet pair. Recombination of independent triplets by exciton–exciton annihilation to form the correlated triplet pair (i.e., nongeminate recombination) happens with 1/3 of the rate of either triplet migration or recombination of the separated correlated triplet pair (geminate recombination).

Until recently, no analytical measure of many-body delocalization in open systems had been developed, yet such a measure enables characterization of how molecular excitons delocalize in photosynthetic light-harvesting complexes, and in turn helps us understand quantum coherent aspects of electronic energy transfer. In this paper we apply these measures to a model peripheral light-harvesting complex, LH2 from Rhodopseudomonas acidophila. We find how many chromophores collectively contribute to the “delocalization length” of an excitation within LH2 and how the coherent delocalization is distributed spatially. We also investigate to what extent this delocalization length is effective, by examining the impact of bipartite and multipartite entanglement in inter-ring energy transfer in LH2.

In this article we study the ultrafast dynamics of excitons and charge carriers photogenerated in two-dimensional in-plane heterostructures, namely, CdSe–CdTe nanoplatelets. We combine transient absorption and two-dimensional electronic spectroscopy to study charge transfer and delocalization from a few tens of femtoseconds to several nanoseconds. In contrast with spherical nanocrystals, the relative alignment of the electron and hole states of CdSe and CdTe in thin 2D nanoplatelets does not lead to a type-II heterostructure. Following the excitation in CdSe or CdTe materials, the electron preferentially delocalises instantaneously over the whole heterostructure. In addition, depending on the crown material (CdTe versus CdTeSe), the hole transfers either to trap states or to the crown, within a few hundreds of femtoseconds. We conclude that the photoluminescence band, at lower energy than the CdSe and CdTe first exciton transition, does not result from the recombination of the charge carriers at the charge transfer state but involves localised hole states.