RESUMO
In this work, the pure rotational spectrum of the vinoxy radical (CH2CHO) has been studied at millimeter and sub-millimeter wavelengths (110-860 GHz). CH2CHO was produced by H-abstraction from acetaldehyde (CH3CHO) using atomic fluorine in a double-pass absorption cell at room temperature. A Zeeman-modulation spectrometer, in which an external magnetic field generated inside the absorption cell is amplitude-modulated, was used to record the pure rotational transitions of the radical. The recorded spectra are devoid of signals from closed-shell species, allowing for relatively fast acquisitions over wide spectral windows. Transitions involving values of the rotational quantum numbers Nâ³ and Kaâ³ up to 41 and 18, respectively, were measured and combined with all available high-resolution literature data (both pure rotation and ground-state combination differences from ro-vibration) to greatly improve the modeling of the CH2CHO spectrum. The combined experimental line list is fit using a semirigid rotor Hamiltonian, and the results are compared to quantum chemical calculations. This laboratory study provides the spectroscopic information needed to search for CH2CHO in various interstellar environments, from cold (e.g., typically 10 K for dense molecular clouds) to warm (e.g., â¼200 K for hot corinos) objects.
RESUMO
Radical species constitute the main reactants of numerous chemical reaction networks occurring in diverse environments. Rotationally resolved laboratory data, essential to undertake the detection of these highly reactive species, remain difficult to obtain using conventional high-resolution spectroscopy techniques. In the present work, we exploit a new experimental setup based on the Faraday rotation detection technique which allows us to study the gas phase spectra of relatively large radicals, such as dehydrogenated complex organic molecules (COMs). We recorded 2086 pure rotational transitions of the acetonyl radical (CH3COCH2) in the 150-450 GHz range, for which no rotational information was previously available. The radical exhibits relatively complex couplings of angular momenta, involving the overall rotation angular momentum, the spin of the unpaired electron, and two large amplitude motions. The data set has been fit using a semirigid Hamiltonian and shows the need for the development of specific theoretical models.
RESUMO
Halide perovskites are versatile semiconductors with applications including photovoltaics and light-emitting devices, having modular optoelectronic properties realizable through composition and dimensionality tuning. Layered Ruddlesden-Popper perovskites are particularly interesting due to their unique 2D character and charge carrier dynamics. However, long-range energy transport through exciton diffusion in these materials is not understood or realized. Here, local time-resolved luminescence mapping techniques are employed to visualize exciton transport in exfoliated flakes of the BA2MAn-1PbnI3n+1 perovskite family. Two distinct transport regimes are uncovered, depending on the temperature range. Above 100 K, diffusion is mediated by thermally activated hopping processes between localized states. At lower temperatures, a nonuniform energy landscape emerges in which transport is dominated by downhill energy transfer to lower-energy states, leading to long-range transport over hundreds of nanometers. Efficient, long-range, and switchable downhill transfer offers exciting possibilities for controlled directional long-range transport in these 2D materials for new applications.
RESUMO
Halide perovskites have shown great potential for light emission and photovoltaic applications due to their remarkable electronic properties. Although the device performances are promising, they are still limited by microscale heterogeneities in their photophysical properties. Here, we study the impact of these heterogeneities on the diffusion of charge carriers, which are processes crucial for efficient collection of charges in light-harvesting devices. A photoluminescence tomography technique is developed in a confocal microscope using one- and two-photon excitation to distinguish between local surface and bulk diffusion of charge carriers in methylammonium lead bromide single crystals. We observe a large dispersion of local diffusion coefficients with values between 0.3 and 2 cm2·s-1 depending on the trap density and the morphological environment-a distribution that would be missed from analogous macroscopic or surface measurements. This work reveals a new framework to understand diffusion pathways, which are extremely sensitive to local properties and buried defects.