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Magnetic properties, crystal structure, and optical resonance of . (a) vs at . (b) XRD patterns at (black line) and (red line), and lattice constant vs temperature (inset). (c) Electron density maps at obtained by MEM. Contours are drawn from . Isosurface is drawn for an equidensity level of , which is drawn pink for clarity. ions exist in the centers of the cavities (see supplemental material18). (d) Imaginary part of the dielectric constant spectra at room temperature, and schematic image of the excitation of the LMCT band (inset).
Photoinduced phase collapse in by blue-light irradiation. (a) XRD patterns at before and after blue-light irradiation, and irradiation time dependence of the phase fraction (inset). (b) Temperature dependence of the phase fraction before irradiation (open circles), during light irradiation at (blue circles), cooling process after irradiation (black circles), and warming process (red circles). (c) Irradiation temperature dependence of the phase fraction before (open circles) and after (black circles) light irradiation for .
Mechanism of the photoinduced phase collapse in . (a) Temperature dependence of calculated Gibbs free energy vs the fraction for based on the Slichter and Drickamer model. Blue and red circles indicate the existing populations of phase and phase, respectively. (b) Schematic picture of the pathway in the photoinduced phase collapse (upper). Temperature dependence of calculated fractions of mainly phase (blue curve) and mainly phase (red curve) for (lower). The bold and narrow lines indicate a thermodynamically stable phase and thermodynamically metastable phase, respectively.
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