Herein,
we report a study of the electronic structure of the ground and first
excited states of Rb2TeCl6, Rb2TeBr6, and Rb2TeI6 halide-perovskite-derived
crystals. Using X-ray photoelectron spectroscopy (XPS) measurements
and density functional theory and multiconfiguration self-consistent
field (MCSCF) calculations, the experimental and theoretical XPS spectra
of the valence region were obtained. In addition, the effects of the
cations and halogen atoms on the electronic structure were determined,
and the classification of the excited states in double point group
representation was carried out. Furthermore, a possible reason for
the luminescence quenching in an isostructural series of crystals
containing the [TeI6]2– anions was determined.
Hollow reduced-symmetry resonant plasmonic nanostructures possess pronounced tunable optical resonances in the UV-vis-IR range, being a promising platform for advanced nanophotonic devices. However, the present fabrication approaches require several consecutive technological steps to produce such nanostructures, making their large-scale fabrication rather time-consuming and expensive. Here, we report on direct single-step fabrication of large-scale arrays of hollow parabolic- and cone-shaped nanovoids in silver and gold thin films, using single-pulse femtosecond nanoablation at high repetition rates. The lateral and vertical size of such nanovoids was found to be laser energy-tunable. Resonant light scattering from individual nanovoids was observed in the visible spectral range, using dark-field confocal microspectroscopy, with the size-dependent resonant peak positions. These colored geometric resonances in far-field scattering were related to excitation and interference of transverse surface plasmon modes in nanovoid shells. Plasmon-mediated electromagnetic field enhancement near the nanovoids was evaluated via finite-difference time-domain calculations for their model shapes simulated by three-dimensional molecular dynamics, and experimentally verified by means of photoluminescence microscopy and Raman spectroscopy.
Using tellurium(IV) complex compounds with outer-sphere ammonium cations as an example, we have studied the interrelation between their geometric structure and spectral-luminescent properties. In the series of compounds of tellurium(IV), which are characterized by the island octahedral coordination of Тe(IV) ions, the luminescence intensity has been found to depend on the degree of distortion of the coordination polyhedron of the Te(IV) ion, the position of the А band in diffuse reflection spectra, and the energy of the luminescence transition 3 P 1 → 1 S 0 of the tellurium(IV) ion. We have revealed that the considered Te(IV) complexes possess reversible thermochromic properties.
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