Leonardo Silvestri

Dielectric tensor of tetracene single crystals: the effect of anisotropy on polarized absorption and emission spectra

The full UV-visible dielectric tensor and the corresponding directions of the principal axes of triclinic tetracene crystals are reported as deduced either by polarized absorption and ellipsometry measurements or by calculations based on the molecular and crystallographic data. The results allow the attribution of the polarized bands observed in both absorption and photoluminescence emission spectra. In particular, the spectral line shape and polarization of the emission are found to depend on the sample thickness, and the effect is attributed to the modification of the state of polarization of the emitted light during its propagation inside the crystal. Indeed, the directions of polarization of the lowest optical transitions and the directions of the principal axes of the dielectric tensor are demonstrated not to coincide, in contrast to the assumptions typically made in the literature, thus causing the mixed transverse/longitudinal character of light propagation.

Reclassifying exciton-phonon coupling in molecular aggregates: Evidence of strong nonadiabatic coupling in oligothiophene crystals

Exciton-phonon (EP) coupling in molecular aggregates is reexamined in cases where extended intermolecular interactions result in low-energy excitons with high effective masses. The analysis is based on a single intramolecular vibrational mode with frequency omega0 and Huang-Rhys factor lambda2. When the curvature Jc at the exciton band bottom is much smaller than the free-exciton Davydov splitting W, the strength of the EP coupling is determined by comparing the nuclear relaxation energy lambda2omega0 with the curvature. In this way, weak (lambda2omega0<<4piJc), intermediate I (lambda2omega0 approximately 4piJc), and strong I (lambda2omega0>>4piJc) coupling regimes are introduced. The conventional intermediate (lambda2omega0 approximately W) and strong (lambda2omega0>>W) EP coupling regimes originally defined by Simpson and Peterson [J. Chem. Phys. 26, 588 (1957)] are based solely on the Davydov splitting and are referred to here as intermediate II and strong II regimes, respectively. Within the intermediate I and strong I regimes the near degeneracy of the low-energy excitons allows efficient nonadiabatic coupling, resulting in a spectral splitting between the b- and ac-polarized first replicas in the vibronic progression characterizing optical absorption. Such spectral signatures are clearly observed in OT4 thin films and crystals, where splittings for the lowest energy mode with omega0=161 cm(-1) are as large as 30 cm(-1) with a small variation due to sample disorder. Numerical calculations using a multiphonon BO basis set and a Hamiltonian including linear EP coupling yield excellent agreement with experiment.

Polarized superradiance from delocalized exciton transitions in tetracene single crystals

Polarized superradiant emission and exciton delocalization in tetracene single crystals are reported. Polarization-, time-, and temperature-resolved spectroscopies evidence the complete polarization of the zero-phonon line of the intrinsic tetracene emission from both the lower (

Hybrid functional study of Si and O donors in wurtzite AlN

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Multiple mode exciton-vibrational coupling in H-aggregates: Synergistic enhancement of the quantum yield

state) and the upper (thermally activated) Davydov excitons. The superradiance of the

Generalized ellipsometry and dielectric tensor of rubrene single crystals

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Chain entanglements and fracture energy in interfaces between immiscible polymers

emission is substantiated by a nearly linear decrease in the radiative lifetime with temperature, being 15 times shorter at 30 K compared to the isolated molecule, with an exciton delocalization of about 40 molecules.

Sensors at Your Fibre Tips: A Novel Liquid Crystal- Based Photonic Transducer for Sensing Systems

The properties of Si and O donors in wurtzite AlN have been studied by means of hybrid functional calculations, finding that both impurities form DX centres. In the case of Si, the stable DX centre is close in energy to the substitutional donor state and to a second metastable DX centre, thus explaining both the persistent effects and the broad range of activation energies observed experimentally. Ionisation energies have been computed for both Si and O donor states.

Polarized absorption, spontaneous and stimulated blue light emission of J-type tetraphenylbutadiene monocrystals.

The impact of exciton-vibrational coupling involving fast and slow vibrational modes on absorption and emission in molecular H-aggregates is investigated using a multimode Holstein Hamiltonian. For H-aggregates composed of rigid molecules the radiative decay rate is rigorously zero due to the asymmetry of the lowest energy exciton. Increasing the Huang-Rhys factors of the coupled modes results in an increase of the radiative efficiency through increased sideband emission. Coupling to a spectrally unresolved slow mode leads to an apparent increase in the 0-0 intensity of the vibronic progression of the fast mode, thereby mimicking a distribution of molecular transition frequencies (diagonal disorder). In the intermediate coupling regime, the radiative efficiency of the aggregate exceeds the sum of the fast-mode-only and slow-mode-only radiative efficiencies. The mechanism underlying the synergistic enhancement of the radiative yield is similar to that which causes spectral splitting in the absorption spectrum of quaterthiophene crystals. [L. Silvestri et al., J. Chem. Phys. 130, 234701 (2009)]. The results here qualitatively account for the robust emission efficiency of hexaphenyl microcrystallites where the slow torsional motion involving the interphenyl dihedral angle in conjunction with the fast ring breathing mode conspire to enhance the quantum yield.

Random lasing in an organic light-emitting crystal and its interplay with vertical cavity feedback

The optical spectra of rubrene single crystals are reported and compared with those of the molecule in solution. From generalized ellipsometry and a proper biaxial model, the complex dielectric tensor is deduced in the spectral region of the excitonic transitions of the crystal between 2.2 eV band 4.4 eV, where the optical bands are assigned and rationalized on the basis of the molecular and crystal symmetries.