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Novel optical pump-push – photocurrent probe ultrafast spectroscopy experiments on organic photoconversion systems show that excessive excitation energy in such systems is not lost but used to reach delocalised states that act as the gateway for long-range charge separation. We also show that the developed experimental approach can be generalised to inorganic and hybrid photoconversion systems.

Singlet fission, the spin-allowed photophysical process converting an excited singlet state into two triplet states, has attracted significant attention for device applications. Research so far has focused mainly on the understanding of singlet fission in pure materials, yet blends offer the promise of a controlled tuning of intermolecular interactions, impacting singlet fission efficiencies. Here we report a study of singlet fission in mixtures of pentacene with weakly interacting spacer molecules. Comparison of experimentally determined stationary optical properties and theoretical calculations indicates a reduction of charge-transfer interactions between pentacene molecules with increasing spacer molecule fraction. Theory predicts that the reduced interactions slow down singlet fission in these blends, but surprisingly we find that singlet fission occurs on a timescale comparable to that in pure crystalline pentacene. We explain the observed robustness of singlet fission in such mixed films by a mechanism of exciton diffusion to hot spots with closer intermolecular spacings.

The interaction between 2,20-bithiophene-5-carboxylic acid (PT2) sublimed under ultra-high vacuum conditions and anatase (101) and rutile (110) TiO2 single crystal surfaces is investigated by studying the electronic spectral density near the Fermi level with synchrotron-based spectroscopy. The experimental results are compared to density functional theory calculations of the isolated PT2 molecule and of the molecule adsorbed on an anatase TiO2 (101) cluster. The relative concentrations of Ti, C, and S atoms indicate that the adsorbed molecule remains intact upon deposition, which is typical of a Stranski-Krastanov growth mode. The analysis of the O1s spectrum suggests a predominant bidentate geometry of the adsorption with both rutile and anatase surfaces, as supported by previous theoretical simulations. It is also theoretically and experimentally demonstrated that the PT2 adsorption causes the appearance of new electronic states in the gap near the TiO2 valence band. A pinning effect of the LUMO level of the dye is also theoretically predicted. [ABSTRACT FROM AUTHOR]

The quantum-chemical study of the electronic and optical properties of unsubstituted oligo(phenylene vinylene) radical cations was reported. The goal is to distinguish the impact of the choice of molecular geometry from the impact of the choice of quantum-chemical method, on the calculated optical transition energies and the optical excitation is localized with HF-CI and delocalized with TD-DFT, almost irrespective of the molecular geometry.

The chain-length dependence of the electronic coupling for photoinduced charge separation in DNA hairpins associated to conjugated linkers, by means of correlated quantum-chemical calculations are explored. Pathways for charge transfer from the linker chromophore to a guanine site located at a well-defined distance along the DNA strand are identified.

Research has been conducted on the photoinduced charge transfer. The quantum-chemical techniques used in investigating the photoinduced charge transfer mechanism and rates are described.

Research is done on the configuration-interaction calculations which are performed to describe the singlet and triplet excited states of oligothiophene and oligo(phenylene ethynylene) conjugated chains. In conclusion, the roles of chain length, heavy-atom derivatization, and ring twists are evaluated.

Conjugated polymers are used in the low-cost fabrication of thin semiconducting films. Over recent years, many polymeric optoelectronic devices have been developed, although it is unclear whether the description of electronic excitations in such materials is more appropriately formed in a molecular or semiconductor picture. Electronic states associated with optical excitations in the conjugated polymer poly(2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene) were studied, using photocurrent measurements and quantum-chemical calculations, and several photocurrent spectral features were found to be coupled with bands in the absorption spectrum.

Configuration interaction calculations on the lowest singlet and triplet excitations in oligothiophenes and their substituted derivatives reveal a decrease in singlet-singlet excitation energies with chain length, and an intersystem crossing between the singlet and triplet forms. This crossing populates the lowest triplet state and creates an absorption red-shift. An extended pi-conjugated path decreases the singlet-singlet excitation energies whereas exchange between two like-spins creates only a marginal effect in the lowest triplet excited state. Geometry relaxation phenomena are also noted.

Here, we present a general approach to treating vibronic coupling in molecular crystals based on atomistic simulations of large clusters. Such clusters comprise model aggregates treated at the quantum chemical level embedded within a realistic environment treated at the molecular mechanics level. As we calculate ground and excited state equilibrium geometries and vibrational modes of model aggregates, our approach is able to capture effects arising from coupling to intermolecular degrees of freedom, absent from existing models relying on geometries and normal modes of single molecules. Using the geometries and vibrational modes of clusters, we are able to simulate the fluorescence spectra of aggregates for which the lowest excited state bears negligible oscillator strength (as is the case, e.g., ideal H-aggregates) by including both Franck-Condon (FC) and Herzberg-Teller (HT) vibronic transitions. The latter terms allow the adiabatic excited state of the cluster to couple with vibrations in a perturbative fashion via derivatives of the transition dipole moment along nuclear coordinates. While vibronic coupling simulations employing FC and HT terms are well established for single-molecules, to our knowledge this is the first time they are applied to molecular aggregates. Here, we apply this approach to the simulation of the low-temperature fluorescence spectrum of para-distyrylbenzene single-crystal H-aggregates and draw comparisons with coarse-grained Frenkel-Holstein approaches previously extensively applied to such systems. [ABSTRACT FROM AUTHOR]

A theory for polarized absorption in crystalline oligoacenes is presented, which includes Frenkel exciton coupling, the coupling between Frenkel and charge-transfer (CT) excitons, and the coupling of all neutral and ionic excited states to the dominant ring-breathing vibrational mode. For tetracene, spectra calculated using all Frenkel couplings among the five lowest energy molecular singlet states predict a Davydov splitting (DS) of the lowest energy (0-0) vibronic band of only -32 cm-1, far smaller than the measured value of 631 cm-1 and of the wrong sign-a negative sign indicating that the polarizations of the lower and upper Davydov components are reversed from experiment. Inclusion of Frenkel-CT coupling dramatically improves the agreement with experiment, yielding a 0-0 DS of 601 cm-1 and a nearly quantitative reproduction of the relative spectral intensities of the 0-n vibronic components. Our analysis also shows that CT mixing increases with the size of the oligoacenes. We discuss the implications of these results on exciton dissociation and transport. [ABSTRACT FROM AUTHOR]

Recent work has suggested that correlations in the environments of chromophores can lead to a change in the dynamics of excitation transfer in both the coherent and incoherent limits. An example of this effect that is relevant to many single molecule experiments occurs in the standard Förster model for resonant energy transfer (RET). The standard formula for the FRET rate breaks down when the electronic excitations on weakly interacting donor and acceptor couple to the same vibrational modes. The transfer rate can then no longer be factored into donor emission and acceptor absorption lineshapes, but must be recast in terms of a renormalized phonon reorganization energy accounting for the magnitude and sign of the excitation-vibration couplings. In this paper, we derive theoretically how the FRET rate depends on the shared mode structure and coupling, examine the simplified case of Gaussian lineshapes and then provide a quantitative calculation for a system of current interest. [ABSTRACT FROM AUTHOR]

Single molecule fluorescence experiments have been performed on a BODIPY-based dye embedded in oligo(styrene) matrices to probe the density fluctuations and the relaxation dynamics of chain segments surrounding the dye molecules. The time-dependent fluorescence lifetime of the BODIPY probe was recorded as an observable for the local density fluctuations. At room temperature, the mean fraction of holes surrounding the probes is shown to be unaffected by the molecular weight in the glassy state. In contrast, the free volume increases significantly in the supercooled regime. These observations are discussed in the framework of the entropic theories of the glass transition. [ABSTRACT FROM AUTHOR]

We have implemented a coupled-cluster equation of motion approach combined with the intermediate neglect of differential overlap parametrization and applied it to study the excited states and optical absorptions in positively and negatively charged conjugated oligomers. The method is found to be both reliable and efficient. The theoretical results are in very good agreement with experiments and confirm that there appear two subgap absorption peaks upon polaron formation. Interestingly, the relative intensities of the polaron-induced subgap absorptions can be related to the extent of the lattice geometry relaxations. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We report a detailed quantum-chemical characterization of the electronic and optical properties of polyfluorene chains and compare them to those in copolymers containing alternating fluorene and benzothiadiazole or ethylenedioxythiophene units. The introduction of the comonomer can strongly modify the excitonic properties as well as the efficiency of charge- and energy-transfer processes. The choice of the comonomer is thus critical in targeting specific optical properties while maintaining good transport properties. [ABSTRACT FROM AUTHOR]

We apply correlated quantum-chemical techniques to study the origin of the large two-photon absorption (TPA) cross sections, δ, in stilbene derivatives in which electron-donating and electron-withdrawing substituents provide a quadrupolar charge-transfer arrangement. An additional field created by a set of point charges is used to systematically modify the ground-state polarization to determine its consequences for the TPA response. The effect on the molecular structure can be quantified by the evolution of the π-bond-order alternation (π-BOA) of the conjugated backbone. For moderate ground-state polarizations, a marked increase of the TPA response occurs; for large polarizations, δ peaks and then drops dramatically. Insight into the origin of this evolution is gained by comparing the values of δ obtained via the converged sum-over-states approach to the results of a simple three-state model. [ABSTRACT FROM AUTHOR]