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1. Valence transition model of the pseudogap, charge order, and superconductivity in electron-doped and hole-doped copper oxides

   https://doi.org/DOI: 10.1103/PhysRevB.98.205153  

   Mazumdar, S. ( October 2018 , Physical review. B, Condensed matter)

   We present a valence transition model for electron- and hole-doped cuprates, within which there occurs a discrete jump in ionicity Cu2+ -> Cu1+ in both families upon doping, at or near optimal doping in the conventionally prepared electron-doped compounds and at the pseudogap phase transition in the hole-doped materials. In thin films of the T' compounds, the valence transition has occurred already in the undoped state. The phenomenology of the valence transition is closely related to that of the neutral-to-ionic transition in mixed-stack organic charge-transfer solids. Doped cuprates have negative charge-transfer gaps, just as rare-earth nickelates and BaBiO3. The unusually high ionization energy of the closed shell Cu1+ ion, taken together with the dopingdriven reduction in three-dimensional Madelung energy and gain in two-dimensional delocalization energy in the negative charge transfer gap state drives the transition in the cuprates. The combined effects of strong correlations and small d-p electron hoppings ensure that the systems behave as effective 1/2-filled Cu band with the closed shell electronically inactive O2- ions in the undoped state, and as correlated two-dimensional geometrically frustrated 1/4-filled oxygen hole band, now with electronically inactive closed-shell Cu1+ ions, in the doped state. The model thus gives microscopic justification for the two-fluid models suggested by many authors. The theory gives the simplest yet most comprehensive understanding of experiments in the normal states. The robust commensurate antiferromagnetism in the conventional T' crystals, the strong role of oxygen deficiency in driving superconductivity and charge carrier sign corresponding to holes at optimal doping are all manifestations of the same quantum state. In the hole-doped pseudogapped state, there occurs a biaxial commensurate period 4 charge density wave state consisting of O1- -Cu l(1+)-O1- spin singlets that coexists with broken rotational C-4 symmetry due to intraunit cell oxygen inequivalence. Finite domains of this broken symmetry state will exhibit twodimensional chirality and the polar Kerr effect. Superconductivity within the model results from a destabilization of the 1/4-filled band paired Wigner crystal [Phys. Rev. B 93, 165110 (2016) and ihid. 93, 205111 (2016)]. We posit that a similar valence transition, Ir4+ -> Ir3+, occurs upon electron doping Sr2IrO4. We make testable experimental predictions in cuprates including superoxygenated La2CuO4+delta and iridates. Finally, as indirect evidence for the valence bond theory of superconductivity proposed here, we note that there exist an unusually large number of unconventional superconductors that exhibit superconductivity proximate to exotic charge ordered states, whose band fillings are universally 1/4 or 3/4, exactly where the paired Wigner crystal is most stable. 

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2. Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition

   https://doi.org/10.5194/acp-18-6331-2018  

   DeRieux, Wing-Sy Wong ; Li, Ying ; Lin, Peng ; Laskin, Julia ; Laskin, Alexander ; Bertram, Allan K. ; Nizkorodov, Sergey A. ; Shiraiwa, Manabu ( January 2018 , Atmospheric Chemistry and Physics)

   Secondary organic aerosol (SOA) accounts for a large fraction of submicron particles in the atmosphere. SOA can occur in amorphous solid or semi-solid phase states depending on chemical composition, relative humidity (RH), and temperature. The phase transition between amorphous solid and semi-solid states occurs at the glass transition temperature (T_g). We have recently developed a method to estimate T_g of pure compounds containing carbon, hydrogen, and oxygen atoms (CHO compounds) with molar mass less than 450 g mol⁻¹ based on their molar mass and atomic O : C ratio. In this study, we refine and extend this method for CH and CHO compounds with molar mass up to ∼ 1100 g mol⁻¹ using the number of carbon, hydrogen, and oxygen atoms. We predict viscosity from the T_g-scaled Arrhenius plot of fragility (viscosity vs. T_g∕T) as a function of the fragility parameter D. We compiled D values of organic compounds from the literature and found that D approaches a lower limit of ∼ 10 (±1.7) as the molar mass increases. We estimated the viscosity of α-pinene and isoprene SOA as a function of RH by accounting for the hygroscopic growth of SOA and applying the Gordon–Taylor mixing rule, reproducing previously published experimental measurements very well. Sensitivity studies were conducted to evaluate impacts of T_g, D, the hygroscopicity parameter (κ), and the Gordon–Taylor constant on viscosity predictions. The viscosity of toluene SOA was predicted using the elemental composition obtained by high-resolution mass spectrometry (HRMS), resulting in a good agreement with the measured viscosity. We also estimated the viscosity of biomass burning particles using the chemical composition measured by HRMS with two different ionization techniques: electrospray ionization (ESI) and atmospheric pressure photoionization (APPI). Due to differences in detected organic compounds and signal intensity, predicted viscosities at low RH based on ESI and APPI measurements differ by 2–5 orders of magnitude. Complementary measurements of viscosity and chemical composition are desired to further constrain RH-dependent viscosity in future studies. 

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3. On the liquid demixing of water + elastin-like polypeptide mixtures: bimodal re-entrant phase behaviour

   https://doi.org/10.1039/d0cp05013j  

   Lindeboom, Tom ; Zhao, Binwu ; Jackson, George ; Hall, Carol K. ; Galindo, Amparo ( March 2021 , Physical Chemistry Chemical Physics)

   null (Ed.)

   Water + elastin-like polypeptides (ELPs) exhibit a transition temperature below which the chains transform from collapsed to expanded states, reminiscent of the cold denaturation of proteins. This conformational change coincides with liquid–liquid phase separation. A statistical-thermodynamics theory is used to model the fluid-phase behavior of ELPs in aqueous solution and to extrapolate the behavior at ambient conditions over a range of pressures. At low pressures, closed-loop liquid–liquid equilibrium phase behavior is found, which is consistent with that of other hydrogen-bonding solvent + polymer mixtures. At pressures evocative of deep-sea conditions, liquid–liquid immiscibility bounded by two lower critical solution temperatures (LCSTs) is predicted. As pressure is increased further, the system exhibits two separate regions of closed-loop of liquid–liquid equilibrium (LLE). The observation of bimodal LCSTs and two re-entrant LLE regions herald a new type of binary global phase diagram: Type XII. At high-ELP concentrations the predicted phase diagram resembles a protein pressure denaturation diagram; possible “molten-globule”-like states are observed at low concentration. 

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4. The potential for aqueous fluid-rock and silicate melt-rock interactions to re-equilibrate hydrogen in peridotite nominally anhydrous minerals

   https://doi.org/10.2138/am-2020-7435  

   Lynn, Kendra J ; Warren, Jessica M ( January 2021 , The American mineralogist)

   Hydrogen is a rapidly diffusing monovalent cation in nominally anhydrous minerals (NAMs, such as olivine, orthopyroxene, and clinopyroxene), which is potentially re-equilibrated during silicate melt-rock and aqueous fluid-rock interactions in massif and abyssal peridotites. We apply a 3D numerical diffusion modeling technique to provide first-order timescales of complete hydrogen re-equilibration in olivine, clinopyroxene, and orthopyroxene over the temperature range 600-1200°C. Model crystals are 1-3 mm along the c-axis and utilize H+ diffusion coefficients appropriate for Fe-bearing systems. Two sets of models were run with different boundary compositions: 1) “low-H models” are constrained by mineral-melt equilibrium partitioning with a basaltic melt that has 0.75 wt% H2O and 2) “high-H models,” which utilize the upper end of the estimated range of mantle water solubility for each phase. Both sets of models yield re-equilibration timescales that are identical and are fast for all phases at a given temperature. These timescales have strong log-linear trends as a function of temperature (R2 from 0.97 to 0.99) that can be used to calculate expected re-equilibration time at a given temperature and grain size. At the high end of the model temperatures (1000-1200°C), H+ completely re-equilibrates in olivine, orthopyroxene, and clinopyroxene within minutes to hours, consistent with previous studies. These short timescales indicate that xenolith NAM mantle water contents are likely to be overprinted prior to eruption. The models also resolve the decoupled water-trace element relationship in Southwest Indian Ridge peridotites, in which peridotite REE abundances are reproduced by partial melting models whereas the relatively high NAM H2O contents require later re-equilibration with melt. At temperatures of 600-800°C, which correspond to conditions of hydrothermal alteration of pyroxene to amphibole and talc, H+ re-equilibration typically occurs over a range of timescales spanning days to years. These durations are well within existing estimates for the duration of fluid flow in oceanic hydrothermal systems, suggesting that peridotite NAM water contents are susceptible to diffusive overprinting during higher temperature hydrothermal alteration. Thus, diffusion during aqueous fluid-rock interactions may also explain NAM H2O contents that are too high to reflect residues of melting. These relatively short timescales at low temperatures suggest that the origin of water contents measured in peridotite NAMs requires additional constraints on sample petrogenesis, including petrographic and trace element analyses. Our 3D model results also hint that H+ may diffuse appreciably during peridotite serpentinization, but diffusion coefficients at low temperature are unconstrained and additional experimental investigations are needed. 

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5. Behavior and properties of water in silicate melts under deep mantle conditions

   https://doi.org/https://doi.org/10.1038/s41598-021-90124-7  

   Karki, Bijaya B ; Ghosh, Dipta B ; Karato, Shun-ichiro ( May 2021 , Scientific reports)

   null (Ed.)

   Water (H2O) as one of the most abundant fluids present in Earth plays crucial role in the generation and transport of magmas in the interior. Though hydrous silicate melts have been studied extensively, the experimental data are confined to relatively low pressures and the computational results are still rare. Moreover, these studies imply large differences in the way water influences the physical properties of silicate magmas, such as density and electrical conductivity. Here, we investigate the equation of state, speciation, and transport properties of water dissolved in Mg1-xFexSiO3 and Mg2(1-x)Fe2xSiO4 melts (for x = 0 and 0.25) as well as in its bulk (pure) fluid state over the entire mantle pressure regime at 2000 to 4000 K using first-principles molecular dynamics. The simulation results allow us to constrain the partial molar volume of the water component in melts along with the molar volume of pure water. The predicted volume of silicate melt+water solution is negative at low pressures and becomes zero above 15 GPa. Consequently, the hydrous component tends to lower the melt density to similar extent over much of the mantle pressure regime irrespective of composition. Our results also show that hydrogen diffuses fast in silicate melts and enhances the melt electrical conductivity in a way that differs from electrical conduction in the bulk water. The speciation of the water component varies considerably from the bulk water structure as well. Water is dissolved in melts mostly as hydroxyls at low pressure and as -O-H-O-, -O-H-O-H- and other extended species with increasing pressure. On the other hand, the pure water behaves as a molecular fluid below 15 GPa, gradually becoming a dissociated fluid with further compression. On the basis of modeled density and conductivity results, we suggest that partial melts containing a few percent of water may be gravitationally trapped both above and below the upper mantle-transition region. Moreover, such hydrous melts can give rise to detectable electrical conductance by means of electromagnetic sounding observations. 

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