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Because methoxyphenols (MP) are emitted in significant quantities during biomass fires and contribute to the secondary organic aerosols formation which impacts the climate, their gas phase monitoring in the atmosphere is crucial and requires accurate rovibrational cross sections determined with a good knowledge of their ground state (GS) and vibrationally excited state (ES) molecular parameters. Therefore, the rotational spectra of the two isomers, 2-MP (guaïacol) and 4-MP (mequinol), have been measured in absorption and in emission at room temperature using a frequency multiplication chain and a mm-wave Fourier transform chirped-pulse spectrometer, respectively. Guided by quantum chemistry calculations, the conformational landscape has been characterised and the observation of only one rotamer in the spectra of 2-MP and 4-MP has been explained. For 2-MP, the most stable conformation is justified by an intramolecular O–H⋯OCH3 hydrogen-bond which has been characterised by a topology analysis of the electron density. In a global fit including more than 30 000 line assignments, rotational and quartic centrifugal constants of the GS and the three lowest energy ES have been determined allowing to reproduce the millimeter-wave spectra at the experimental accuracy. The same work has been performed on the cis-rotamer of 4-MP highlighting some perturbations marring the fit quality for two vibrationally ES. Finally, the isomeric dependence of the negative inertial defect ΔI agrees with that of the lowest energy out of plane mode ν45, and the variation of ΔI with the degree of vibrational excitation allows a fine estimation of v45 = 1 vibrational wavenumber. [ABSTRACT FROM AUTHOR]

Neuromorphic computing, reconfigurable optical metamaterials that are operational over a wide spectral range, holographic and nonvolatile displays of extremely high resolution, integrated smart photonics, and many other applications need next-generation phase-change materials (PCMs) with better energy efficiency and wider temperature and spectral ranges to increase reliability compared to current flagship PCMs, such as Ge 2 Sb 2 Te 5 or doped Sb 2 Te. Gallium tellurides are favorable compounds to achieve the necessary requirements because of their higher melting and crystallization temperatures, combined with low switching power and fast switching rate. Ga 2 Te 3 and non-stoichiometric alloys appear to be atypical PCMs; they are characterized by regular tetrahedral structures and the absence of metavalent bonding. The sp 3 gallium hybridization in cubic and amorphous Ga 2 Te 3 is also different from conventional p-bonding in flagship PCMs, raising questions about its phase-change mechanism. Furthermore, gallium tellurides exhibit a number of unexpected and highly unusual phenomena, such as nanotectonic compression and viscosity anomalies just above their melting points. Using high-energy X-ray diffraction, supported by first-principles simulations, we will elucidate the atomic structure of amorphous Ga 2 Te 5 PLD films, compare it with the crystal structure of tetragonal gallium pentatelluride, and investigate the electrical, optical, and thermal properties of these two materials to assess their potential for memory applications, among others.

High-capacity solid-state batteries are promising future products for large-scale energy storage and conversion. Sodium fast ion conductors including glasses and glass ceramics are unparalleled materials for these applications. Rational design and tuning of advanced sodium sulfide electrolytes need a deep insight into the atomic structure and dynamics in relation with ion-transport properties. Using pulsed neutron diffraction and Raman spectroscopy supported by first-principles simulations, we show that preferential diffusion pathways in vitreous sodium and silver sulfides are related to isolated sulfur S iso , that is, the sulfur species surrounded exclusively by mobile cations with a typical stoichiometry of M/S iso ≈ 2. The S iso /S tot fraction appears to be a reliable descriptor of fast ion transport in glassy sulfide systems over a wide range of ionic conductivities and cation diffusivities. The S iso fraction increases with mobile cation content x , tetrahedral coordination of the network former and, in case of thiogermanate systems, with germanium disulfide metastability and partial disproportionation, GeS 2 → GeS + S, leading to the formation of additional sulfur, transforming into S iso . A research strategy enabling to achieve extended and interconnected pathways based on isolated sulfur would lead to glassy electrolytes with superior ionic diffusion.

Binary Ge-Te and ternary Ge-Sb-Te systems belong to flagship phase-change materials (PCMs) and are used in nonvolatile memory applications and neuromorphic computing. The working temperatures of these PCMs are limited by low- T glass transition and crystallization phenomena. Promising high- T PCMs may include gallium tellurides; however, the atomic structure and transformation processes for amorphous Ga-Te binaries are simply missing. Using high-energy X-ray diffraction and Raman spectroscopy supported by first-principles simulations, we elucidate the short- and intermediate-range order in bulk glassy Ga x Te 1- x , 0.17 ≤ x ≤ 0.25, following their thermal, electric, and optical properties, revealing a semiconductor-metal transition above melting. We also show that a phase change in binary Ga-Te is characterized by a very unusual nanotectonic compression with the high internal transition pressure reaching 4-8 GPa, which appears to be beneficial for PCM applications increasing optical and electrical contrast between the SET and RESET states and decreasing power consumption.

Phase-change materials based on tellurides are widely used for optical storage (DVD and Blu-ray disks), non-volatile random access memories and for development of neuromorphic computing. Narrow-gap tellurides are intrinsically limited in the telecom spectral window, where materials having a wider gap are needed. Here we show that gallium sulfide GaS thin films prepared by pulsed laser deposition reveal good transparency from the visible to the mid-IR spectral range with optical gap Eg = 2.34 eV, high refractive index nR = 2.50 over the 0.8 ≤ λ ≤ 2.5 μm range and, unlike canonical chalcogenide glasses, the absence of photo-structural transformations with a laser-induced peak power density damage threshold above 1.4 TW cm-2 at 780 nm. The origin of the excellent damage threshold under a high-power laser and UV light irradiation resides in the rigid tetrahedral structure of vitreous GaS studied by high-energy X-ray diffraction and Raman spectroscopy and supported by first-principles simulations. The average local coordination number appears to be m = 3.44, well above the optimal connectivity, 2.4 ≤ m ≤ 2.7, and the total volume of microscopic voids and cavities is 34.4%, that is, lower than for the vast majority of binary sulfide glasses. The glass-crystal phase transition in gallium sulfide thin films may be accompanied by a drastic change in the nonlinear optical properties, opening up a new dimension for memory applications in the visible to mid-IR spectral ranges.

Sodium-conducting sulfide glasses are promising materials for the next generation of solid-state batteries. Deep insight into the glass structure is required to ensure a functional design and tailoring of vitreous alloys for energy applications. Using pulsed neutron diffraction supported by first-principles molecular dynamics, we show a structural diversity of Na 2 S-As 2 S 3 sodium thioarsenate glasses, consisting of long corner-sharing (CS) pyramidal chains CS-(AsSS 2/2 ) k , small As p S q rings ( p + q ≤ 11), mixed corner- and edge-sharing oligomers, edge-sharing (ES) dimers ES-As 2 S 4 , and isolated (ISO) pyramids ISO-AsS 3 , entirely or partially connected by sodium species. Polysulfide S-S bridges and structural units with homopolar As-As bonds complete the glass structure, which is basically different from structural motifs predicted by the equilibrium phase diagram. In contrast to superionic silver and sodium sulfide glasses, characterized by a significant population of isolated sulfur species S iso (0.20 < S iso /S tot < 0.28), that is, sulfur connected to only mobile cations M + with a usual M/S iso stoichiometry of 2, poorly conducting Na 2 S-As 2 S 3 alloys exhibit a modest S iso fraction of 6.2%.

Room temperature millimeter-wave rotational spectroscopy supported by high level of theory calculations have been employed to fully characterise the conformational landscape of 3-Methoxyphenol, a semi-volatile polar oxygenated aromatic compound precursor of secondary organic aerosols in the atmosphere arising from biomass combustion. While previous rotationally-resolved spectroscopic studies in the microwave and in the UV domains failed to observe the complete conformational landscape, the 70-330 GHz rotational spectrum measured in this study reveals the ground state rotational signatures of the four stable conformations theoretically predicted. Moreover, rotational transitions in the lowest energy vibrationally excited states were assigned for two conformers. While the inertial defect of methoxyphenol does not significantly change between conformers and isomers, the excitation of the methoxy out-of-plane bending is the main contribution to the non-planarity of the molecule., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The ν 2 and ν 5 fundamental bands of thionyl chloride (SOCl 2 ) were measured in the 420 cm -1 -550 cm -1 region using the FT-far-IR spectrometer exploiting synchrotron radiation on the AILES beamline at SOLEIL. A straightforward line-by-line analysis is complicated by the high congestion of the spectrum due to both the high density of SOCl 2 rovibrational bands and the presence of the ν 2 fundamental band of sulfur dioxide produced by hydrolysis of SOCl 2 with residual water. To overcome this difficulty, our assignment procedure for the main isotopologues 32 S 16 O 35 Cl 2 and 32 S 16 O 35 Cl 37 Cl alternates between a direct fit of the spectrum, via a global optimization technique, and a traditional line-by-line analysis. The global optimization, based on an evolutionary algorithm, produces rotational constants and band centers that serve as useful starting values for the subsequent spectroscopic analysis. This work helped to identify the pure rotational submillimeter spectrum of 32 S 16 O 35 Cl 2 in the v 2 =1 and v 5 =1 vibrational states of Martin-Drumel et al. [J. Chem. Phys. 144, 084305 (2016)]. As a by-product, the rotational transitions of the v 4 =1 far-IR inactive state were identified in the submillimeter spectrum. A global fit gathering all the microwave, submillimeter, and far-IR data of thionyl chloride has been performed, showing that no major perturbation of rovibrational energy levels occurs for the main isotopologue of the molecule.