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    Even harmonic generation in isotropic media of dissociating homonuclear molecules
    ([London] : Macmillan Publishers Limited, part of Springer Nature, 2016) Silva, R.E.F.; Rivière, P.; Morales, F.; Smirnova, O.; Ivanov, M.; Martín, F.
    Isotropic gases irradiated by long pulses of intense IR light can generate very high harmonics of the incident field. It is generally accepted that, due to the symmetry of the generating medium, be it an atomic or an isotropic molecular gas, only odd harmonics of the driving field can be produced. Here we show how the interplay of electronic and nuclear dynamics can lead to a marked breakdown of this standard picture: a substantial part of the harmonic spectrum can consist of even rather than odd harmonics. We demonstrate the effect using ab-initio solutions of the time-dependent Schrödinger equation for and its isotopes in full dimensionality. By means of a simple analytical model, we identify its physical origin, which is the appearance of a permanent dipole moment in dissociating homonuclear molecules, caused by light-induced localization of the electric charge during dissociation. The effect arises for sufficiently long laser pulses and the region of the spectrum where even harmonics are produced is controlled by pulse duration. Our results (i) show how the interplay of femtosecond nuclear and attosecond electronic dynamics, which affects the charge flow inside the dissociating molecule, is reflected in the nonlinear response, and (ii) force one to augment standard selection rules found in nonlinear optics textbooks by considering light-induced modifications of the medium during the generation process.
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    Surface effects of vapour-liquid-solid driven Bi surface droplets formed during molecular-beam-epitaxy of GaAsBi
    ([London] : Macmillan Publishers Limited, part of Springer Nature, 2016) Steele, J.A.; Lewis, R.A.; Horvat, J.; Nancarrow, M.J.B.; Henini, M.; Fan, D.; Mazur, Y.I.; Schmidbauer, M.; Ware, M.E.; Yu, S.-Q.; Salamo, G.J.
    Herein we investigate a (001)-oriented GaAs1−xBix/GaAs structure possessing Bi surface droplets capable of catalysing the formation of nanostructures during Bi-rich growth, through the vapour-liquid-solid mechanism. Specifically, self-aligned “nanotracks” are found to exist trailing the Bi droplets on the sample surface. Through cross-sectional high-resolution transmission electron microscopy the nanotracks are revealed to in fact be elevated above surface by the formation of a subsurface planar nanowire, a structure initiated mid-way through the molecular-beam-epitaxy growth and embedded into the epilayer, via epitaxial overgrowth. Electron microscopy studies also yield the morphological, structural and chemical properties of the nanostructures. Through a combination of Bi determination methods the compositional profile of the film is shown to be graded and inhomogeneous. Furthermore, the coherent and pure zincblende phase property of the film is detailed. Optical characterisation of features on the sample surface is carried out using polarised micro-Raman and micro-photoluminescence spectroscopies. The important light producing properties of the surface nanostructures are investigated through pump intensity-dependent micro-PL measurements, whereby relatively large local inhomogeneities are revealed to exist on the epitaxial surface for important optical parameters. We conclude that such surface effects must be considered when designing and fabricating optical devices based on GaAsBi alloys.
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    Tailoring optical properties and stimulated emission in nanostructured polythiophene
    ([London] : Macmillan Publishers Limited, part of Springer Nature, 2019) Portone, Alberto; Ganzer, Lucia; Branchi, Federico; Ramos, Rodrigo; Caldas, Marília J.; Pisignano, Dario; Molinari, Elisa; Cerullo, Giulio; Persano, Luana; Prezzi, Deborah; Virgili, Tersilla
    Polythiophenes are the most widely utilized semiconducting polymers in organic electronics, but they are scarcely exploited in photonics due to their high photo-induced absorption caused by interchain polaron pairs, which prevents the establishment of a window of net optical gain. Here we study the photophysics of poly(3-hexylthiophene) configured with different degrees of supramolecular ordering, spin-coated thin films and templated nanowires, and find marked differences in their optical properties. Transient absorption measurements evidence a partially-polarized stimulated emission band in the nanowire samples, in contrast with the photo-induced absorption band observed in spin-coated thin films. In combination with theoretical modeling, our experimental results reveal the origin of the primary photoexcitations dominating the dynamics for different supramolecular ordering, with singlet excitons in the nanostructured samples superseding the presence of polaron pairs, which are present in the disordered films. Our approach demonstrates a viable strategy to direct optical properties through structural control, and the observation of optical gain opens the possibility to the use of polythiophene nanostructures as building blocks of organic optical amplifiers and active photonic devices. © 2019, The Author(s).