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The emerging CdTe–BeTe semiconductor alloy that exhibits a dramatic mismatch in bond covalency and bond stiffness clarifying its vibrational-mechanical properties is used as a benchmark to test the limits of the percolation model (PM) worked out to explain the complex Raman spectra of the related but less contrasted Zn1−xBex-chalcogenides. The test is done by way of experiment ( x ≤ 0.11 ), combining Raman scattering with X-ray diffraction at high pressure, and ab initio calculations (x ~ 0–0.5; x ~1). The (macroscopic) bulk modulus B 0 drops below the CdTe value on minor Be incorporation, at variance with a linear B 0 versus x increase predicted ab initio, thus hinting at large anharmonic effects in the real crystal. Yet, no anomaly occurs at the (microscopic) bond scale as the regular bimodal PM-type Raman signal predicted ab initio for Be–Te in minority (x ~0, 0.5) is barely detected experimentally. At large Be content (x ~1), the same bimodal signal relaxes all the way down to inversion, an unprecedented case. However, specific pressure dependencies of the regular (x ~0, 0.5) and inverted (x ~1) Be–Te Raman doublets are in line with the predictions of the PM. Hence, the PM applies as such to Cd1−xBexTe without further refinement, albeit in a "relaxed" form. This enhances the model's validity as a generic descriptor of phonons in alloys. [ABSTRACT FROM AUTHOR]

Raman scattering and ab initio Raman/phonon calculations, supported by X-ray diffraction, are combined to study the vibrational properties of Zn1−xBexTe under pressure. The dependence of the Be–Te (distinct) and Zn–Te (compact) Raman doublets that distinguish between Be- and Zn-like environments is examined within the percolation model with special attention to x ~ (0,1). The Be-like environment hardens faster than the Zn-like one under pressure, resulting in the two sub-modes per doublet getting closer and mechanically coupled. When a bond is so dominant that it forms a matrix-like continuum, its two submodes freely couple on crossing at the resonance, with an effective transfer of oscillator strength. Post resonance the two submodes stabilize into an inverted doublet shifted in block under pressure. When a bond achieves lower content and merely self-connects via (finite/infinite) treelike chains, the coupling is undermined by overdamping of the in-chain stretching until a «phonon exceptional point» is reached at the resonance. Only the out-of-chain vibrations «survive» the resonance, the in-chain ones are «killed». This picture is not bond-related, and hence presumably generic to mixed crystals of the closing-type under pressure (dominant over the opening-type), indicating a key role of the mesostructure in the pressure dependence of phonons in mixed crystals. [ABSTRACT FROM AUTHOR]