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Sub-micrometer particle size effects on metastable phases for a photoswitchable Co–Fe Prussian blue analog

Metastable phases of the photoswitchable molecular magnet K0.3Co[Fe(CN)6]0.77 ⋅  nH2O in sub-micrometer particles have been structurally investigated by synchrotron powder x-ray diffraction (PXRD) measurements. The K0.3Co[Fe(CN)6]0.77 ⋅  nH2O bulk compound (studied here with a sample having average particle size of 500 nm) undergoes a charge transfer coupled spin transition (CTCST), where spin configurations change between a paramagnetic CoII( S = 3/2) –FeIII( S = 1/2) high-temperature (HT) state and a diamagnetic CoIII( S = 0) –FeII( S = 0) low-temperature (LT) state. The bulk compound exhibits a unique intermediate (IM) phase, which corresponds to a mixture of HT and LT spin states that depend on the cooling rate. Several hidden metastable HT states emerge as a function of thermal and photo stimuli, namely: (1) a quench (Q) state generated from the HT state by flash cooling, (2) a LTPX state obtained by photoexcitation from the LT state derived by thermal relaxation from the Q state, and (3) an IMPX state accessed by photo-irradiation from the IM state. A sample with a smaller particle size, 135 nm, is investigated for which the particles are on the scale of the coherent LT domains in the IM phase within the larger 500 nm sample. PXRD studies under controlled thermal and/or optical excitations have clarified that the more »

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NSF-PAR ID:
10363309
Journal Name:
Journal of Applied Physics
Volume:
131
Issue:
8
Page Range or eLocation-ID:
Article No. 085110
ISSN:
0021-8979
Publisher:
American Institute of Physics
2. ABSTRACT We present a systematic investigation of physical conditions and elemental abundances in four optically thick Lyman-limit systems (LLSs) at z = 0.36–0.6 discovered within the cosmic ultraviolet baryon survey (CUBS). Because intervening LLSs at z < 1 suppress far-UV (ultraviolet) light from background QSOs, an unbiased search of these absorbers requires a near-UV-selected QSO sample, as achieved by CUBS. CUBS LLSs exhibit multicomponent kinematic structure and a complex mix of multiphase gas, with associated metal transitions from multiple ionization states such as C ii, C iii, N iii, Mg ii, Si ii, Si iii, O ii, O iii, O vi, and Fe ii absorption that span several hundred km s−1 in line-of-sight velocity. Specifically, higher column density components (log N(H i)/cm−2≳ 16) in all four absorbers comprise dynamically cool gas with $\langle T \rangle =(2\pm 1) \times 10^4\,$K and modest non-thermal broadening of $\langle b_\mathrm{nt} \rangle =5\pm 3\,$km s−1. The high quality of the QSO absorption spectra allows us to infer the physical conditions of the gas, using a detailed ionization modelling that takes into account the resolved component structures of H i and metal transitions. The range of inferred gas densities indicates that these absorbers consist of spatially compact clouds with a median line-of-sight thickness of $160^{+140}_{-50}$ pc. While obtaining robust metallicitymore »