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- ItemMetallofullerene photoswitches driven by photoinduced fullerene-to-metal electron transfer(Cambridge : RSC, 2021) Zalibera, Michal; Ziegs, Frank; Schiemenz, Sandra; Dubrovin, Vasilii; Lubitz, Wolfgang; Savitsky, Anton; Deng, Shihu H.M.; Wang, Xue-Bin; Advoshenko, Stanislav M.; Popov, Alexey A.We report on the discovery and detailed exploration of the unconventional photo-switching mechanism in metallofullerenes, in which the energy of the photon absorbed by the carbon cage π-system is transformed to mechanical motion of the endohedral cluster accompanied by accumulation of spin density on the metal atoms. Comprehensive photophysical and electron paramagnetic resonance (EPR) studies augmented by theoretical modelling are performed to address the phenomenon of the light-induced photo-switching and triplet state spin dynamics in a series of YxSc3−xN@C80 (x = 0–3) nitride clusterfullerenes. Variable temperature and time-resolved photoluminescence studies revealed a strong dependence of their photophysical properties on the number of Sc atoms in the cluster. All molecules in the series exhibit temperature-dependent luminescence assigned to the near-infrared thermally-activated delayed fluorescence (TADF) and phosphorescence. The emission wavelengths and Stokes shift increase systematically with the number of Sc atoms in the endohedral cluster, whereas the triplet state lifetime and S1–T1 gap decrease in this row. For Sc3N@C80, we also applied photoelectron spectroscopy to obtain the triplet state energy as well as the electron affinity. Spin distribution and dynamics in the triplet states are then studied by light-induced pulsed EPR and ENDOR spectroscopies. The spin–lattice relaxation times and triplet state lifetimes are determined from the temporal evolution of the electron spin echo after the laser pulse. Well resolved ENDOR spectra of triplets with a rich structure caused by the hyperfine and quadrupolar interactions with 14N, 45Sc, and 89Y nuclear spins are obtained. The systematic increase of the metal contribution to the triplet spin density from Y3N to Sc3N found in the ENDOR study points to a substantial fullerene-to-metal charge transfer in the excited state. These experimental results are rationalized with the help of ground-state and time-dependent DFT calculations, which revealed a substantial variation of the endohedral cluster position in the photoexcited states driven by the predisposition of Sc atoms to maximize their spin population.
- ItemTwo-photon, visible light water splitting at a molecular ruthenium complex(Cambridge : RSC Publ., 2021) Schneidewind, Jacob; Argüello Cordero, Miguel A.; Junge, Henrik; Lochbrunner, Stefan; Beller, MatthiasWater splitting to give molecular oxygen and hydrogen or the corresponding protons and electrons is a fundamental four-electron redox process, which forms the basis of photosynthesis and is a promising approach to convert solar into chemical energy. Artificial water splitting systems have struggled with orchestrating the kinetically complex absorption of four photons as well as the difficult utilization of visible light. Based on a detailed kinetic, spectroscopic and computational study of Milstein's ruthenium complex, we report a new mechanistic paradigm for water splitting, which requires only two photons and offers a new method to extend the range of usable wavelengths far into the visible region. We show that two-photon water splitting is enabled by absorption of the first, shorter wavelength photon, which produces an intermediate capable of absorbing the second, longer wavelength photon (up to 630 nm). The second absorption then causes O–O bond formation and liberation of O2. Theoretical modelling shows that two-photon water splitting can be used to achieve a maximum solar-to-hydrogen efficiency of 18.8%, which could be increased further to 28.6% through photochemical instead of thermal H2 release. It is therefore possible to exceed the maximum efficiency of dual absorber systems while only requiring a single catalyst. Due to the lower kinetic complexity, intrinsic utilization of a wide wavelength range and high-performance potential, we believe that this mechanism will inspire the development of a new class of water splitting systems that go beyond the reaction blueprint of photosynthesis.
- ItemLow-energy constraints on photoelectron spectra measured from liquid water and aqueous solutions(Cambridge : RSC Publ., 2021) Malerz, Sebastian; Trinter, Florian; Hergenhahn, Uwe; Ghrist, Aaron; Ali, Hebatallah; Nicolas, Christophe; Saak, Clara-Magdalena; Richter, Clemens; Hartweg, Sebastian; Nahon, Laurent; Lee, Chin; Goy, Claudia; Neumark, Daniel M; Meijer, Gerard; Wilkinson, Iain; Winter, Bernd; Thürmer, StephanWe report on the effects of electron collision and indirect ionization processes, occurring at photoexcitation and electron kinetic energies well below 30 eV, on the photoemission spectra of liquid water. We show that the nascent photoelectron spectrum and, hence, the inferred electron binding energy can only be accurately determined if electron energies are large enough that cross sections for quasi-elastic scattering processes, such as vibrational excitation, are negligible. Otherwise, quasi-elastic scattering leads to strong, down-to-few-meV kinetic energy scattering losses from the direct photoelectron features, which manifest in severely distorted intrinsic photoelectron peak shapes. The associated cross-over point from predominant (known) electronically inelastic to quasi-elastic scattering seems to arise at surprisingly large electron kinetic energies, of approximately 10–14 eV. Concomitantly, we present evidence for the onset of indirect, autoionization phenomena (occurring via superexcited states) within a few eV of the primary and secondary ionization thresholds. These processes are inferred to compete with the direct ionization channels and primarily produce low-energy photoelectrons at photon and electron impact excitation energies below ∼15 eV. Our results highlight that vibrational inelastic electron scattering processes and neutral photoexcitation and autoionization channels become increasingly important when photon and electron kinetic energies are decreased towards the ionization threshold. Correspondingly, we show that for neat water and aqueous solutions, great care must be taken when quantitatively analyzing photoelectron spectra measured too close to the ionization threshold. Such care is essential for the accurate determination of solvent and solute ionization energies as well as photoelectron branching ratios and peak magnitudes.
- ItemHigh-order parametric generation of coherent XUV radiation(Washington, DC : Soc., 2021) Hort, O.; Dubrouil, A.; Khokhlova, M.A.; Descamps, D.; Petit, S.; Burgy, F.; Mével, E.; Constant, E.; Strelkov, V.V.Extreme ultraviolet (XUV) radiation finds numerous applications in spectroscopy. When the XUV light is generated via high-order harmonic generation (HHG), it may be produced in the form of attosecond pulses, allowing access to unprecedented ultrafast phenomena. However, the HHG efficiency remains limited. Here we present an observation of a new regime of coherent XUV emission which has a potential to provide higher XUV intensity, vital for applications. We explain the process by high-order parametric generation, involving the combined emission of THz and XUV photons, where the phase matching is very robust against ionization. This introduces a way to use higher-energy driving pulses, thus generating more XUV photons.
- ItemCoherent interaction of atoms with a beam of light confined in a light cage(London : Nature Publishing Group, 2021) Davidson-Marquis, Flavie; Gargiulo, Julian; Gómez-López, Esteban; Jang, Bumjoon; Kroh, Tim; Müller, Chris; Ziegler, Mario; Maier, Stefan A.; Kübler, Harald; Schmidt, Markus A.; Benson, OliverControlling coherent interaction between optical fields and quantum systems in scalable, integrated platforms is essential for quantum technologies. Miniaturised, warm alkali-vapour cells integrated with on-chip photonic devices represent an attractive system, in particular for delay or storage of a single-photon quantum state. Hollow-core fibres or planar waveguides are widely used to confine light over long distances enhancing light-matter interaction in atomic-vapour cells. However, they suffer from inefficient filling times, enhanced dephasing for atoms near the surfaces, and limited light-matter overlap. We report here on the observation of modified electromagnetically induced transparency for a non-diffractive beam of light in an on-chip, laterally-accessible hollow-core light cage. Atomic layer deposition of an alumina nanofilm onto the light-cage structure was utilised to precisely tune the high-transmission spectral region of the light-cage mode to the operation wavelength of the atomic transition, while additionally protecting the polymer against the corrosive alkali vapour. The experiments show strong, coherent light-matter coupling over lengths substantially exceeding the Rayleigh range. Additionally, the stable non-degrading performance and extreme versatility of the light cage provide an excellent basis for a manifold of quantum-storage and quantum-nonlinear applications, highlighting it as a compelling candidate for all-on-chip, integrable, low-cost, vapour-based photon delay.
- ItemFirst stellar photons for an integrated optics discrete beam combiner at the William Herschel Telescope(Washington, DC : The Optical Society, 2021) Nayak, Abani Shankar; Labadie, Lucas; Sharma, Tarun Kumar; Piacentini, Simone; Corrielli, Giacomo; Osellame, Roberto; Gendron, Éric; Buey, Jean-Tristan M.; Chemla, Fanny; Cohen, Mathieu; Bharmal, Nazim A.; Bardou, Lisa F.; Staykov, Lazar; Osborn, James; Morris, Timothy J.; Pedretti, Ettore; Dinkelaker, Aline N.; Madhav, Kalaga V.; Roth, Martin M.We present the first on-sky results of a four-telescope integrated optics discrete beam combiner (DBC) tested at the 4.2mWilliamHerschel Telescope. The device consists of a four-input pupil remapper followed by a DBC and a 23-output reformatter. The whole device was written monolithically in a single alumino-borosilicate substrate using ultrafast laser inscription. The device was operated at astronomical H-band (1.6 μm), and a deformable mirror along with a microlens array was used to inject stellar photons into the device. We report the measured visibility amplitudes and closure phases obtained on Vega and Altair that are retrieved using the calibrated transfer matrix of the device. While the coherence function can be reconstructed, the on-sky results show significant dispersion from the expected values. Based on the analysis of comparable simulations, we find that such dispersion is largely caused by the limited signal-to-noise ratio of our observations. This constitutes a first step toward an improved validation of theDBCas a possible beam combination scheme for long-baseline interferometry. © 2021 Optical Society of America.
- ItemPhoton-electron coincidence experiments at synchrotron radiation facilities with arbitrary bunch modes([S.l.] : American Institute of Physics, 2021) Ozga, C.; Honisch, C.; Schmidt, P.; Holzapfel, X.; Zindel, C.; Küstner-Wetekam, C.; Richter, C.; Hergenhahn, U.; Ehresmann, A.; Knie, A.; Hans, A.We report the adaptation of an electron–photon coincidence detection scheme to the multibunch hybrid mode of the synchrotron radiation source BESSY II (Helmholtz-Zentrum Berlin). Single-event-based data acquisition and evaluation, combined with the use of relative detection times between the coincident particles, enable the acquisition of proper coincidence signals from a quasi-continuous excitation pattern. The background signal produced by accidental coincidences in the time difference representation is modeled using the non-coincident electron and photon spectra. We validate the method by reproducing previously published results, which were obtained in the single bunch mode, and illustrate its usability for the multibunch hybrid mode by investigating the photoionization of CO2 into CO+2 B satellite states, followed by subsequent photon emission. The radiative lifetime obtained and the electron binding energy are in good agreement with earlier publications. We expect this method to be a useful tool to extend the versatility of coincident particle detection to arbitrary operation modes of synchrotron radiation facilities and other excitation sources without the need for additional experimental adjustments.