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Crystal-like atomic arrangement and optical properties of 25La$$_{2}$$O$$_{3}$$-75MoO$$_{3}$$ binary glasses composed of isolated MoO$$_{4}$$$$^{2-}$$

Masuno, Atsunobu*; Munakata, Sae*; Okamoto, Yoshihiro  ; Yaji, Toyonari*; Kosugi, Yoshihisa*; Shimakawa, Yuichi*

Transparent and brown La$$_{2}$$O$$_{3}$$-MoO$$_{3}$$ binary glasses were prepared in bulk form using a levitation technique. The glass-forming range was limited, with the primary composition being approximately 25 mol% La$$_{2}$$O$$_{3}$$. This glass exhibited a clear crystallization at 546 $$^{circ}$$C, while determining its glass transition temperature was difficult. Notably, despite its amorphous nature, the glass possessed a density and packing density comparable to those of crystalline La$$_{2}$$Mo$$_{3}$$O$$_{12}$$. X-ray absorption fine structure and Raman scattering analyses revealed that the glass structure closely resembles La$$_{2}$$Mo$$_{3}$$O$$_{12}$$ due to the presence of isolated MoO$$_{4}$$$$^{2-}$$ units, whereas disordered atomic arrangement around La atoms was confirmed. The glass demonstrated transparency ranging from 378 to 5500 nm, and the refractive index at 1.0 $$mu$$m was estimated to be 2.0. The optical bandgap energy was 3.46 eV, which was slightly smaller than that of La$$_{2}$$Mo$$_{3}$$O$$_{12}$$. Additionally, the glass displayed a transparent region ranging from 6.5 to 8.0 $$mu$$m. This occurrence results from the decreased diversity of MoO$$_{n}$$ units and connectivity of Mo-O-Mo, which resulted in the reduced overlap of multiphonon absorption. This glass formation, with its departure from conventional glass-forming rules, resulted in distinctive glasses with crystal-like atomic arrangements.

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Category:Chemistry, Inorganic & Nuclear

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