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1.
Chem Commun (Camb) ; 60(8): 1047, 2024 Jan 23.
Article in English | MEDLINE | ID: mdl-38223922

ABSTRACT

Retraction of 'Carbon content drives high temperature superconductivity in a carbonaceous sulfur hydride below 100 GPa' by G. Alexander Smith et al., Chem. Commun., 2022, 58, 9064-9067, https://doi.org/10.1039/D2CC03170A.

3.
Philos Trans A Math Phys Eng Sci ; 381(2258): 20220346, 2023 Oct 16.
Article in English | MEDLINE | ID: mdl-37634534

ABSTRACT

We have analysed [Formula: see text] with a combination of synchrotron X-ray diffraction and X-ray absorption spectroscopy across a pressure range of [Formula: see text] GPa with thermal annealing by a [Formula: see text] laser allowing access to all of the known high-density polymorphs of [Formula: see text], and here report their crystallographic information. The metastability of the post-rutile [Formula: see text]-[Formula: see text] and [Formula: see text] structures in [Formula: see text] are investigated by experiment and PW-DFT simulations, revealing a complex energetic landscape and suggesting a significant dependence of the observed phases on the pressure-temperature pathway taken in experiment. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 1)'.

4.
Rev Sci Instrum ; 93(8): 083901, 2022 Aug 01.
Article in English | MEDLINE | ID: mdl-36050120

ABSTRACT

We present a portable CO2 laser heating system for in situ x-ray absorption spectroscopy (XAS) studies at 16-BM-D (High Pressure Collaborative Access Team, Advanced Photon Source, Argonne National Laboratory). Back scattering optical measurements are made possible by the implementation of a Ge beamsplitter. Optical pyrometry is conducted in the near-infrared, and our temperature measurements are free of chromatic aberration due to the implementation of the peak-scaling method [A. Kavner and W. R. Panero, Phys. Earth Planet. Inter. 143-144, 527-539 (2004) and A. Kavner and C. Nugent, Rev. Sci. Instrum. 79, 024902 (2008)] and mode scrambling of the input signal. Laser power stabilization is established using electronic feedback, providing a steady power over second timescales [Childs et al., Rev. Sci. Instrum. 91, 103003 (2020)]-crucial for longer XAS collections. Examples of in situ high pressure-temperature extended x-ray absorption fine structure measurements of ZrO2 are presented to demonstrate this new capability.

5.
Chem Commun (Camb) ; 58(65): 9064-9067, 2022 Aug 11.
Article in English | MEDLINE | ID: mdl-35837875

ABSTRACT

We report a previously unobserved superconducting state of the photosynthesized carbonaceous sulfur hydride (C-S-H) system with a maximum TC of 191(1) K below 100 GPa. The properties of C-S-H are dependent on carbon content, and X-ray diffraction and simulations reveal the system remains molecular-like up to 100 GPa.

6.
Chem Commun (Camb) ; 58(46): 6634-6637, 2022 Jun 08.
Article in English | MEDLINE | ID: mdl-35587042

ABSTRACT

TcS2 undergoes a charge transfer insulator to metal transition above 28 GPa. Laser annealing reveals a kinetically hindered high pressure arsenopyrite phase that is recoverable to ambient. The new phase is similar to the Mn-dichalcogenides rather than the expected Re-dichalcogenides and involves the formation of S-S and Tc-Tc bonds.

7.
Phys Rev Lett ; 127(1): 016401, 2021 Jul 02.
Article in English | MEDLINE | ID: mdl-34270285

ABSTRACT

A reversible density driven insulator to metal to insulator transition in high-spin MnS_{2} is experimentally observed, leading with a colossal electrical resistance drop of 10^{8} Ω by 12 GPa. Density functional theory simulations reveal the metallization to be unexpectedly driven by previously unoccupied S_{2}^{2-} σ_{3p}^{*} antibonding states crossing the Fermi level. This is a unique variant of the charge transfer insulator to metal transition for negative charge transfer insulators having anions with an unsaturated valence. By 36 GPa the emergence of the low-spin insulating arsenopyrite (P2_{1}/c) is confirmed, and the bulk metallicity is broken with the system returning to an insulative electronic state.

8.
J Phys Chem Lett ; 10(18): 5351-5356, 2019 Sep 19.
Article in English | MEDLINE | ID: mdl-31436423

ABSTRACT

Many rutile-type materials are characterized by a softness in shear with pressure which is coupled to a Raman-active librational motion. Combining direct studies of anion positions in SnO2 with measurements of its electronic properties, we find a correlation between O sublattice disorder between 5 and 10 GPa and an anomalous decrease up to 4 orders of magnitude in electrical resistance. Hypotheses into the atomistic nature of the phenomenon are evaluated via ab initio calculations guided by extended X-ray absorption fine structure spectroscopy analysis, and the most likely mechanism is found to be the displacement of single anions resulting from the pressure-induced softening of the librational mode. On the basis of this mechanism, we propose that the same behavior should feature across all materials exhibiting a rutile → CaCl2 phase transition and that conductivity in other rutile-type materials could be facilitated at ambient pressure by appropriate design of devices to enhance defects of this nature.

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