Molecular overtones and two-phonon combination bands in the near-infrared spectra of talc, brucite and lizardite

The near-infrared (NIR) spectra of hydrous minerals display absorption bands involving multiple excitations of vibrational modes. They usually involve OH stretching modes, but their interpretation is not straightforward due to the combined effects of bond anharmonicity and vibrational coupling. In the present study, the mid-infrared (MIR) and near-infrared spectra of well-ordered samples of trioctahedral layered hydrous minerals, talc, brucite and lizardite, have been measured on a spectral range extending from the fundamental vibrational modes to the second OH stretching overtones. The bands corresponding to molecular overtones are interpreted using an effective approach allowing us to infer the anharmonicity and coupling parameters controlling the OH stretching frequencies from spectroscopic data. They follow the usual relation between transition energy and quantum number of the excited state, which facilitates the comparison of NIR and MIR spectra. The results support the assignment of the main overtone bands to specific environments of OH groups and bring new constraints for the identification of the vibrational bands related to Fe and Al substitutions at octahedral sites in serpentines. The two-phonon absorption bands are theoretically analyzed at the density functional theory level by computing the absorption arising from the self-energy of the IR-active vibrational modes. The characteristics of the two-phonon OH stretching continuum between 7300 and 7400 cm−1 and of the combination bands between 4000 and 4800 cm−1 are related to the specificities of the one-phonon and two-phonon densities of states of the three minerals.</p

Melting curve and phase diagram of ammonia monohydrate at high pressure and temperature

International audienceThe phase diagram and melting behavior of the equimolar water-ammonia mixture have been investigated by Raman spectroscopy, x-ray diffraction, and visual observations from 295 K to 675 K and up to 9 GPa. Our results show non-congruent melting behavior of ammonia monohydrate (AMH) solid below 324 K and congruent melting at higher temperatures. The congruent melting is associated with the stability of a previously unobserved solid phase of AMH, which we named AMH-VII. Another, presumably water-rich, hydrate has also been detected in the range 4 GPa-7 GPa at 295 K on decompression of the high pressure disordered ionico-molecular alloy (DIMA) phase. Comparing our melting data to the literature suggests that non-congruent melting extends from 220 K to 324 K and that the solid phase that borders the fluid between 220 K and 270 K, called AMH-III, is not a proper phase of AMH but a solid solution of ammonia hemihydrate and ice. These results allow us to propose a revised and extended experimental phase diagram of AMH. Published under license by AIP Publishing. https://doi.org/10.1063/5.0021207 .,

Synthesis and characterisation of a new graphitic C–S compound obtained by high pressure decomposition of CS2

International audienceCarbon disulphide (CS2) is, together with its closest analogue CO2, one of the simplest molecular systems made of double covalent bonds. Under high pressure, the molecular structure is expected to break up to form extended crystalline or polymeric solids. Here we show that by compression at 300 K to ∼10 GPa (100 kbar) using large-volume high pressure techniques, a sudden reaction leads to a mixture of pure sulphur and a well-defined compound with stoichiometry close to C2S which can be recovered to ambient pressure. We present neutron and x-ray diffraction as well as Raman data which show that this material consists of sulphur bonded to sp2 graphite layers of nanometric dimensions. The compound is a semiconductor with a gap of 45 meV, as revealed by temperature dependent resistivity measurements, and annealing at temperatures above 200 °C allows to reduce its sulphur content up to C10S. Its structural and electronic properties are fundamentally different to “Bridgman black” reported from previous high pressure experiments on CS2

Topologically frustrated ionisation in a water-ammonia ice mixture

Water and ammonia are major constituents of icy planet interiors, however their phase behaviour under extreme conditions remain relatively unknown. Here, the authors show that ammonia monohydrate transforms under pressure into an alloy composed of molecules as well as ions, owing to a topological frustration

Vibrational-mechanical properties of the highly-mismatched Cd1−xBexTe semiconductor alloy: experiment and ab initio calculations

Abstract 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 ( $$x\le 0.11$$ x ≤ 0.11 ), combining Raman scattering with X-ray diffraction at high pressure, and ab initio calculations ( $$x$$ x  ~ 0–0.5; $$x$$ x ~1). The (macroscopic) bulk modulus $${B}_{0}$$ B 0 drops below the CdTe value on minor Be incorporation, at variance with a linear $${B}_{0}$$ B 0 versus $$x$$ 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 ( $$x$$ x ~0, 0.5) is barely detected experimentally. At large Be content ( $$x$$ x ~1), the same bimodal signal relaxes all the way down to inversion, an unprecedented case. However, specific pressure dependencies of the regular ( $$x$$ x ~0, 0.5) and inverted ( $$x$$ 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

Rheology of colloidal particles in lyotropic hexagonal liquid crystals: the role of particle loading, shape, and phase transition kinetics

The rheology of self-assembled elongated iron oxyhydroxide (FeOOH) and spherical silica (SiO2) particles in hexagonal (H1) liquid crystal (LC) phase of water and non-ionic surfactant C12E9 is investigated by varying particle concentration and cooling rate. The rheology data shows that both SiO2/H1 and FeOOH/ H1 LC composites exhibit a higher G′ when compared to the particle-free H1 phase, with increasing particle loading and cooling rate. FeOOH particles improve G′ of the H1 phase more significantly than SiO2 particles due to the formation of an interconnected network at H1 domain boundaries at cooling rates of 1 and 2 ∘C/min. We hypothesize that self-assembly of particles at domain boundaries leads to a decreased mobility of defects causing an increase in elasticity of particle-laden H1 phase. Dynamic strain sweep and creep experiments show a non-linear stress–strain relationship attributed to the alignment of micellar cylindrical rods under shear.by Siddharth Kulkarni and Prachi Tharej

Suspensions of titania nanoparticle networks in nematic liquid crystals: rheology and microstructure

We study the influence of confinement on the rheology and structure of nematic liquid crystals (NLCs). NLCs get confined in networks of titania (TiO2, primary particle size = 21 nm) nanoparticles in suspensions of TiO2 and NLC, N-(4-methoxybenzylidene)-4-butylaniline (MBBA). Suspensions with TiO2 nanoparticle volume fraction (ϕ) of 0.006–0.017, form viscoelastic solids with low elastic modulus (G′) of 101 Pa–102 Pa and short relaxation times. Increase in TiO2 nanoparticle ϕ leads to a rise in G′ with TiO2 nanoparticles forming a percolating network at a critical volume fraction (ϕ c) = 0.023, and G′ of ~103 Pa. TiO2/MBBA NLC suspensions at and above ϕ c = 0.023 show G′ ~ ω x−1 scaling, where ω is the angular frequency and the minimum in loss modulus (G′′) with ω. The effective noise temperature, x decreases and approaches 1 with the increase in the TiO2 nanoparticle ϕ from 0.023–0.035, is indicative of an increase in the glassy dynamics. Through the polarized light microscopy and differential scanning calorimetry experiments, we propose that the progressive addition of TiO2 nanoparticles introduces a quenched random disorder (QRD) in the NLC medium which disturbs the nematic order. This results in metastable TiO2/MBBA NLC suspensions in which NLC domains get confined in the network of flocs of TiO2 nanoparticles. We also show that the salient rheological signatures of soft glassy rheology develop only in the presence of NLC MBBA and are absent in the isotropic phase of MBBA.by Siddharth Kulkarni and Prachi Tharej