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Thermally Initiated Formation of Criegee Intermediate CH 2 OO in the Oxidation of Ethane

Criegee intermediates (CIs) play an important role in atmospheric chemistry as a transient source of the OH radical through their formation by the ozonolysis of unsaturated organic compounds. Here, we report thermally initiated formation of the smallest CI (CH 2 OO) in the oxidation of ethane (CH 3 CH 3 ) that may be relevant to combustion and flames. The SiO 2 /SiC oxidation microreactor is heated to 1800 K and has a short residence time of ∼100 μs. The CH 2 OO we observe is likely formed in a lower-temperature region near the microreactor’s exit. Plausible mechanisms for CH 2 OO formation and retention under these conditions mediated by methylperoxy (CH 3 OO) radicals are discussed. Pure rotational spectra of CH 2 OO and other intermediates (HO 2 , CH 3 CHO, CH 2 CHOH, c-CH 2 OCH 2 , CH 3 CH 2 CHO, CH 3 OOH, and HCOOH) are detected with a chirped-pulse Fourier transform millimeter-wave spectrometer operating in the frequency range of 60–90 GHz. In conclusion, detection occurs in a molecular beam, where the species are supersonically cooled to 5 K.

Hydrocarbons↗

Materials Data on Ho7Rh3 by Materials Project

Ho7Rh3 crystallizes in the hexagonal P6_3mc space group. The structure is three-dimensional. there are three inequivalent Ho sites. In the first Ho site, Ho is bonded in a 3-coordinate geometry to three equivalent Rh atoms. All Ho–Rh bond lengths are 2.80 Å. In the second Ho site, Ho is bonded in a distorted L-shaped geometry to two equivalent Rh atoms. Both Ho–Rh bond lengths are 2.82 Å. In the third Ho site, Ho is bonded in a 3-coordinate geometry to three equivalent Rh atoms. All Ho–Rh bond lengths are 2.87 Å. Rh is bonded in a 6-coordinate geometry to six Ho atoms.

36 MATERIALS SCIENCE↗

Materials Data on LiMn3Al2(HO2)6 by Materials Project

LiAl2(HO)6(MnO2)3 crystallizes in the monoclinic C2/m space group. The structure is two-dimensional and consists of one LiAl2(HO)6 sheet oriented in the (0, 0, 1) direction and one MnO2 sheet oriented in the (0, 0, 1) direction. In the LiAl2(HO)6 sheet, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share edges with six equivalent AlO6 octahedra. There are four shorter (2.10 Å) and two longer (2.14 Å) Li–O bond lengths. Al3+ is bonded to six O2- atoms to form AlO6 octahedra that share edges with three equivalent LiO6 octahedra and edges with three equivalent AlO6 octahedra. There is four shorter (1.91 Å) and two longer (1.93 Å) Al–O bond length. There are two inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. In the second H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a 1-coordinate geometry to one Li1+, two equivalent Al3+, and one H1+ atom. In the second O2- site, O2- is bonded in a 1-coordinate geometry to one Li1+, two equivalent Al3+, and one H1+ atom. In the MnO2 sheet, there are two inequivalent Mn+3.67+ sites. In the first Mn+3.67+ site, Mn+3.67+ is bonded to six O2- atoms to form edge-sharing MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.92–1.97 Å. In the second Mn+3.67+ site, Mn+3.67+ is bonded to six O2- atoms to form edge-sharing MnO6 octahedra. There are four shorter (1.98 Å) and two longer (2.15 Å) Mn–O bond lengths. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a 4-coordinate geometry to three Mn+3.67+ atoms. In the second O2- site, O2- is bonded in a 3-coordinate geometry to three Mn+3.67+ atoms.

36 MATERIALS SCIENCE↗

Evolution of Physical Properties of RE 3 Ni 5 Al 19 Family (RE = Y, Nd, Sm, Gd, Tb, Dy, Ho, and Er)

In this study, single crystals of RE 3 Ni 5 Al 19 series (RE = Y, Nd, Sm, Gd, Tb, Dy, Ho, and Er) are grown using the Al self-flux method. The crystal structure is examined by both single crystal and powder X-ray diffraction. Physical properties are studied for the first time for RE 3 Ni 5 Al 19 (RE = Y, Nd, Gd, Tb, Dy, Ho, and Er) by means of magnetic susceptibility, electrical resistivity, and heat capacity measurements. Complex magnetic behaviors, with up to three transitions present for RE = Sm, Gd, Tb, and Dy, are revealed. Y 3 Ni 5 Al 19 is found to be a nonmagnetic nonsuperconducting metal (above T = 1.8 K) with weak electron–phonon coupling strength.

36 MATERIALS SCIENCE↗

Collaborative Research Proposal: Time Resolved Optical Emissions Spectroscopy and Laser Induced Fluorescence Spectroscopy of Nanosecond Pulsed Discharges in a Gas-Liquid Water Film Reactor

Electrical discharge plasma formed in contact with liquid water is of interest for a wide range of applications in chemical, biomedical, agricultural, electrical, and materials science and engineering. Such plasma reactors are of very timely importance since they also have significant disinfection capability by inactivating bacteria, viruses and other pathogens. Many types of plasma sources including those driven by AC, DC, RF, microwave, and pulsed electrical power supplies coupled to a wide range of different electrode configurations and reactor designs have been developed and explored which contact the plasma with liquid water. Recent roadmaps have recommended that further work is needed to develop our understanding of the fundamental chemical and physical process which occur at the interface of non-thermal plasma with liquid water solutions in order to advance this large diversity of applications which ultimately depend upon efficient production of key reactive chemical species. There is a wide range of interacting factors that affect the chemical reactions that occur in the plasma, in the liquid phase, and at the interface. These factors ultimately govern the key reactive chemical species formed and used in the various applications and they include a) the reactor design and input parameters, b) the discharge and transport processes, c) the plasma properties, and d) the resulting chemical reactions. For pulsed discharges, the power supply design and output parameters control the applied voltage, frequency, rise time, and width (duration) of the applied pulses. The reactor design involves specification of the gas-liquid contacting methods, electrode gap distance, reactor volume and shape, and gas and liquid flow rates achievable. The gas and liquid compositions as well as the liquid properties such as pH and conductivity are also of key importance in determination of the resulting chemical reactions. In addition, the important plasma properties include plasma gas temperature, electron density, electron energy (distribution), and size of the plasma channels which are all affected by the discharge and transport properties. Many studies have focused on specific aspects of these various processes. Of particular important and relevance to the proposed work is the utilization of nanosecond pulses to generate plasma in gas-liquid systems, liquid bubbles, underwater, and in gases. Recent advances in nanosecond pulses provide significant advantages in utilization with liquid water. For example, fast rise time and short pulses are less sensitive to water conductivity, such short pulses may provide advantages in fast temporal quenching of the plasma, and fundamental analysis of pulse properties, including pulse shape and width, may be facilitated by investigation of single filamentary fast pulses. Many studies have also dealt with the role of the gas composition on formation of reactive oxygen species (ROS) (i.e., hydroxyl radicals – ·OH, hydrogen peroxide – H 2 O 2 , various atomic oxygen species, ozone-O 3 , hydroperoxyl radicals HO 2 ·) and reactive nitrogen species (RNS) (i.e., nitrogen oxides – NO, NO 2 , N 2 O - collectively termed NO X , nitrite-NO 2 - , nitrate-NO 3 - , peroxynitrite-ONOO - ). The hydroxyl radical is the critical species in many chemical oxidation reactions for chemical degradation of toxic compounds in water and gases and for synthesis of some compounds. The mixture of various nitrogen oxide species is important for many biochemical and biological processes involved in biomedical and agricultural applications including disinfection and fertilizer production. The present proposal focuses on determination of the effects of time resolved electron density and hydroxyl radicals on plasma chemical reactions through collaboration with the Princeton Collaborative Low Temperature Plasma Research Facility (PCRF) at the Princeton Plasma Physics Laboratory (PPPL). In order to further investigate the role of the plasma generated electrons and hydroxyl radicals on the overall formation of the key species including hydrogen peroxide, hydroxyl radicals, and nitrogen oxides, the proposed work, thus seeks to determine high resolution time resolved electron density by optical emissions spectroscopy and time resolved hydroxyl radicals using laser induced fluorescence in the nanosecond discharge reactor. The combination of data on electron density and hydroxyl radical concentration will be utilized in the present work to more fully characterize the chemical reaction processes in this system and to advance the design, development, and operation of such chemical reactors for a wide range of applications.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Crystal Growth and Elemental Homogeneity of the Multicomponent Rare-Earth Garnet (Lu 1/6 Y 1/6 Ho 1/6 Dy 1/6 Tb 1/6 Gd 1/6 ) 3 Al 5 O 12

We report high-entropy aluminum garnets were grown as bulk single crystals using the micro-pulling-down method, taking the synthesis of complex ceramics a step further from the conventional preparation of polycrystalline materials. We studied the effects of growth parameters on the elemental distribution in high optical quality crystals of (Lu 1/6 Y 1/6 Ho 1/6 Dy 1/6 Tb 1/6 Gd 1/6 ) 3 Al 5 O 12 containing six cations (yttrium and rare-earths) taken in equimolar amounts. A single garnet structure was confirmed by powder X-ray diffraction. Electron microprobe measurements were obtained to correlate the radial distribution of rare-earth elements with pulling rates and molten zone height. The nature of the elemental distribution in the radial direction was associated with ionic radius: smaller rare-earths concentrated in the center of the crystal, while larger rare-earths segregated toward the outer edge of the cylindrical crystal. Faster pulling rates led to a flattening of the concentration profiles toward the nominal concentration, promoting a more homogeneous radial elemental distribution, while varying the molten zone height did not have a significant effect. The demonstrated success with crystal growth enables the practical availability of single crystals of multicomponent aluminum garnets for further discovery of new phenomena and applications.

36 MATERIALS SCIENCE↗

Materials Data on Ho20In40Rh19 by Materials Project

Ho20Rh19In40 crystallizes in the tetragonal P-4m2 space group. The structure is three-dimensional. there are five inequivalent Ho sites. In the first Ho site, Ho is bonded in a 4-coordinate geometry to four equivalent Rh and eight In atoms. All Ho–Rh bond lengths are 3.00 Å. There are four shorter (3.28 Å) and four longer (3.46 Å) Ho–In bond lengths. In the second Ho site, Ho is bonded in a 4-coordinate geometry to four Rh and eight In atoms. There are two shorter (3.02 Å) and two longer (3.05 Å) Ho–Rh bond lengths. There are two shorter (3.34 Å) and six longer (3.35 Å) Ho–In bond lengths. In the third Ho site, Ho is bonded in a 3-coordinate geometry to four Rh and ten In atoms. There are a spread of Ho–Rh bond distances ranging from 3.06–3.58 Å. There are a spread of Ho–In bond distances ranging from 3.18–3.73 Å. In the fourth Ho site, Ho is bonded in a 2-coordinate geometry to two equivalent Rh and five In atoms. Both Ho–Rh bond lengths are 2.90 Å. There are a spread of Ho–In bond distances ranging from 3.11–3.40 Å. In the fifth Ho site, Ho is bonded in a 2-coordinate geometry to two equivalent Rh and seven In atoms. Both Ho–Rh bond lengths are 2.93 Å. There are a spread of Ho–In bond distances ranging from 3.11–3.44 Å. There are six inequivalent Rh sites. In the first Rh site, Rh is bonded in a 9-coordinate geometry to five Ho and five In atoms. There are a spread of Rh–In bond distances ranging from 2.82–2.86 Å. In the second Rh site, Rh is bonded in a 10-coordinate geometry to three Ho and six In atoms. There are a spread of Rh–In bond distances ranging from 2.73–2.98 Å. In the third Rh site, Rh is bonded in a 8-coordinate geometry to eight In atoms. There are four shorter (2.72 Å) and four longer (2.88 Å) Rh–In bond lengths. In the fourth Rh site, Rh is bonded in a 8-coordinate geometry to eight In atoms. There are four shorter (2.74 Å) and four longer (2.88 Å) Rh–In bond lengths. In the fifth Rh site, Rh is bonded in a distorted hexagonal bipyramidal geometry to eight In atoms. There are four shorter (2.69 Å) and four longer (2.89 Å) Rh–In bond lengths. In the sixth Rh site, Rh is bonded in a 10-coordinate geometry to three Ho and six In atoms. There are a spread of Rh–In bond distances ranging from 2.73–2.97 Å. There are nine inequivalent In sites. In the first In site, In is bonded in a 2-coordinate geometry to two equivalent Ho, two Rh, and one In atom. The In–In bond length is 3.23 Å. In the second In site, In is bonded in a 3-coordinate geometry to two equivalent Ho, three Rh, and one In atom. The In–In bond length is 3.22 Å. In the third In site, In is bonded in a 3-coordinate geometry to four Ho and three Rh atoms. In the fourth In site, In is bonded in a 2-coordinate geometry to two equivalent Ho and two equivalent Rh atoms. In the fifth In site, In is bonded in a 11-coordinate geometry to four Ho, three Rh, and two equivalent In atoms. Both In–In bond lengths are 3.31 Å. In the sixth In site, In is bonded in a 3-coordinate geometry to six Ho and three Rh atoms. In the seventh In site, In is bonded in a 11-coordinate geometry to four Ho, three Rh, and two equivalent In atoms. Both In–In bond lengths are 3.31 Å. In the eighth In site, In is bonded in a 2-coordinate geometry to five Ho, three Rh, and five In atoms. Both In–In bond lengths are 3.25 Å. In the ninth In site, In is bonded in a 7-coordinate geometry to five Ho, three Rh, and five In atoms.

36 MATERIALS SCIENCE↗

Materials Data on Ho4RuBr5 by Materials Project

Ho4RuBr5 crystallizes in the tetragonal P4_2/nnm space group. The structure is three-dimensional. there are three inequivalent Ho sites. In the first Ho site, Ho is bonded to three equivalent Ru and three Br atoms to form a mixture of corner and edge-sharing HoRu3Br3 octahedra. The corner-sharing octahedra tilt angles range from 2–15°. There are two shorter (2.81 Å) and one longer (2.83 Å) Ho–Ru bond lengths. There are one shorter (3.06 Å) and two longer (3.19 Å) Ho–Br bond lengths. In the second Ho site, Ho is bonded to one Ru and five Br atoms to form distorted HoRuBr5 octahedra that share corners with three HoRu3Br3 octahedra and edges with eight HoRuBr5 octahedra. The corner-sharing octahedra tilt angles range from 2–15°. The Ho–Ru bond length is 2.68 Å. There are a spread of Ho–Br bond distances ranging from 2.90–3.22 Å. In the third Ho site, Ho is bonded to one Ru and five Br atoms to form distorted HoRuBr5 octahedra that share a cornercorner with one HoRu3Br3 octahedra and edges with eight HoRuBr5 octahedra. The corner-sharing octahedral tilt angles are 14°. The Ho–Ru bond length is 2.70 Å. There are a spread of Ho–Br bond distances ranging from 2.92–3.19 Å. Ru is bonded to six Ho atoms to form distorted edge-sharing RuHo6 octahedra. There are four inequivalent Br sites. In the first Br site, Br is bonded in a distorted see-saw-like geometry to four Ho atoms. In the second Br site, Br is bonded in a distorted see-saw-like geometry to four Ho atoms. In the third Br site, Br is bonded in a 3-coordinate geometry to three Ho atoms. In the fourth Br site, Br is bonded in a 3-coordinate geometry to three Ho atoms.

36 MATERIALS SCIENCE↗

Materials Data on Ho5Cl11 by Materials Project

Ho5Cl11 crystallizes in the monoclinic P2_1/m space group. The structure is three-dimensional. there are six inequivalent Ho sites. In the first Ho site, Ho is bonded in a 7-coordinate geometry to seven Cl atoms. There are a spread of Ho–Cl bond distances ranging from 2.68–3.13 Å. In the second Ho site, Ho is bonded to seven Cl atoms to form distorted edge-sharing HoCl7 pentagonal bipyramids. There are a spread of Ho–Cl bond distances ranging from 2.63–2.93 Å. In the third Ho site, Ho is bonded in a 6-coordinate geometry to seven Cl atoms. There are a spread of Ho–Cl bond distances ranging from 2.62–3.30 Å. In the fourth Ho site, Ho is bonded in a 8-coordinate geometry to eight Cl atoms. There are a spread of Ho–Cl bond distances ranging from 2.61–3.01 Å. In the fifth Ho site, Ho is bonded in a 7-coordinate geometry to seven Cl atoms. There are a spread of Ho–Cl bond distances ranging from 2.65–3.21 Å. In the sixth Ho site, Ho is bonded in a 8-coordinate geometry to eight Cl atoms. There are a spread of Ho–Cl bond distances ranging from 2.65–2.97 Å. There are twelve inequivalent Cl sites. In the first Cl site, Cl is bonded in a distorted trigonal planar geometry to three Ho atoms. In the second Cl site, Cl is bonded to four Ho atoms to form distorted corner-sharing ClHo4 trigonal pyramids. In the third Cl site, Cl is bonded in a distorted bent 150 degrees geometry to two Ho atoms. In the fourth Cl site, Cl is bonded in a 3-coordinate geometry to three Ho atoms. In the fifth Cl site, Cl is bonded in a distorted trigonal non-coplanar geometry to three Ho atoms. In the sixth Cl site, Cl is bonded in a distorted rectangular see-saw-like geometry to four Ho atoms. In the seventh Cl site, Cl is bonded in a 3-coordinate geometry to three Ho atoms. In the eighth Cl site, Cl is bonded in a trigonal planar geometry to three Ho atoms. In the ninth Cl site, Cl is bonded in a distorted T-shaped geometry to three Ho atoms. In the tenth Cl site, Cl is bonded to four Ho atoms to form a mixture of distorted edge and corner-sharing ClHo4 tetrahedra. In the eleventh Cl site, Cl is bonded in a bent 120 degrees geometry to two Ho atoms. In the twelfth Cl site, Cl is bonded in a distorted rectangular see-saw-like geometry to four Ho atoms.

36 MATERIALS SCIENCE↗

Materials Data on HoIn2Pd by Materials Project

HoPdIn2 crystallizes in the tetragonal I4mm space group. The structure is three-dimensional. there are four inequivalent Ho sites. In the first Ho site, Ho is bonded in a 2-coordinate geometry to four Pd and nine In atoms. There are a spread of Ho–Pd bond distances ranging from 3.09–3.67 Å. There are a spread of Ho–In bond distances ranging from 3.14–3.46 Å. In the second Ho site, Ho is bonded in a 3-coordinate geometry to four Pd and eight In atoms. There are a spread of Ho–Pd bond distances ranging from 3.06–3.25 Å. There are a spread of Ho–In bond distances ranging from 3.19–3.54 Å. In the third Ho site, Ho is bonded in a 12-coordinate geometry to four equivalent Pd and eight In atoms. All Ho–Pd bond lengths are 3.23 Å. There are four shorter (3.28 Å) and four longer (3.36 Å) Ho–In bond lengths. In the fourth Ho site, Ho is bonded in a 4-coordinate geometry to four equivalent Pd and eight In atoms. All Ho–Pd bond lengths are 2.97 Å. There are four shorter (3.35 Å) and four longer (3.38 Å) Ho–In bond lengths. There are three inequivalent Pd sites. In the first Pd site, Pd is bonded in a 10-coordinate geometry to four Ho and six In atoms. There are a spread of Pd–In bond distances ranging from 2.78–2.91 Å. In the second Pd site, Pd is bonded in a 8-coordinate geometry to two equivalent Ho and eight In atoms. There are a spread of Pd–In bond distances ranging from 2.81–2.86 Å. In the third Pd site, Pd is bonded in a 10-coordinate geometry to five Ho and five In atoms. There are a spread of Pd–In bond distances ranging from 2.81–2.88 Å. There are four inequivalent In sites. In the first In site, In is bonded in a 11-coordinate geometry to six Ho, three Pd, and two equivalent In atoms. Both In–In bond lengths are 3.17 Å. In the second In site, In is bonded in a 3-coordinate geometry to five Ho and three Pd atoms. In the third In site, In is bonded in a 7-coordinate geometry to four Ho, three Pd, and one In atom. In the fourth In site, In is bonded in a 3-coordinate geometry to two equivalent Ho and three Pd atoms.

36 MATERIALS SCIENCE↗

Materials Data on HoNiAs by Materials Project

HoNiAs is hexagonal omega structure-derived structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. there are two inequivalent Ho sites. In the first Ho site, Ho is bonded to six equivalent Ni and six equivalent As atoms to form a mixture of edge and face-sharing HoNi6As6 cuboctahedra. All Ho–Ni bond lengths are 2.93 Å. All Ho–As bond lengths are 3.07 Å. In the second Ho site, Ho is bonded to six equivalent Ni and six equivalent As atoms to form a mixture of edge and face-sharing HoNi6As6 cuboctahedra. All Ho–Ni bond lengths are 3.13 Å. All Ho–As bond lengths are 2.98 Å. Ni is bonded in a 3-coordinate geometry to six Ho and three equivalent As atoms. All Ni–As bond lengths are 2.34 Å. As is bonded in a 3-coordinate geometry to six Ho and three equivalent Ni atoms.

36 MATERIALS SCIENCE↗

Materials Data on Ho11Cd45 by Materials Project

Ho11Cd45 is Bergman Structure: Mg32(Al,Zn)49 Bergman-derived structured and crystallizes in the cubic F-43m space group. The structure is three-dimensional. there are five inequivalent Ho sites. In the first Ho site, Ho is bonded in a 8-coordinate geometry to fourteen Cd atoms. There are a spread of Ho–Cd bond distances ranging from 3.13–3.39 Å. In the second Ho site, Ho is bonded in a 12-coordinate geometry to fourteen Cd atoms. There are a spread of Ho–Cd bond distances ranging from 3.16–3.80 Å. In the third Ho site, Ho is bonded in a 4-coordinate geometry to sixteen Cd atoms. There are four shorter (3.25 Å) and twelve longer (3.36 Å) Ho–Cd bond lengths. In the fourth Ho site, Ho is bonded in a 3-coordinate geometry to sixteen Cd atoms. There are a spread of Ho–Cd bond distances ranging from 3.25–3.52 Å. In the fifth Ho site, Ho is bonded in a 10-coordinate geometry to sixteen Cd atoms. There are a spread of Ho–Cd bond distances ranging from 3.13–3.66 Å. There are fourteen inequivalent Cd sites. In the first Cd site, Cd is bonded in a 9-coordinate geometry to five Ho and eight Cd atoms. There are a spread of Cd–Cd bond distances ranging from 3.01–3.11 Å. In the second Cd site, Cd is bonded in a 4-coordinate geometry to four equivalent Ho and twelve equivalent Cd atoms. All Cd–Cd bond lengths are 3.35 Å. In the third Cd site, Cd is bonded to three Ho and nine Cd atoms to form a mixture of distorted corner, edge, and face-sharing CdHo3Cd9 cuboctahedra. There are a spread of Cd–Cd bond distances ranging from 2.79–3.16 Å. In the fourth Cd site, Cd is bonded in a 8-coordinate geometry to four Ho and four Cd atoms. There are two shorter (2.89 Å) and two longer (3.02 Å) Cd–Cd bond lengths. In the fifth Cd site, Cd is bonded to four Ho and eight Cd atoms to form a mixture of distorted corner, edge, and face-sharing CdHo4Cd8 cuboctahedra. There are a spread of Cd–Cd bond distances ranging from 2.81–3.32 Å. In the sixth Cd site, Cd is bonded in a 3-coordinate geometry to three Ho and eight Cd atoms. There are a spread of Cd–Cd bond distances ranging from 3.00–3.27 Å. In the seventh Cd site, Cd is bonded in a 12-coordinate geometry to four Ho and eight Cd atoms. Both Cd–Cd bond lengths are 3.21 Å. In the eighth Cd site, Cd is bonded in a 11-coordinate geometry to three equivalent Ho and eight Cd atoms. There are one shorter (3.01 Å) and one longer (3.13 Å) Cd–Cd bond lengths. In the ninth Cd site, Cd is bonded in a 11-coordinate geometry to four Ho and seven Cd atoms. The Cd–Cd bond length is 3.02 Å. In the tenth Cd site, Cd is bonded in a 12-coordinate geometry to three Ho and nine Cd atoms. In the eleventh Cd site, Cd is bonded in a distorted body-centered cubic geometry to four Ho and four Cd atoms. In the twelfth Cd site, Cd is bonded in a distorted body-centered cubic geometry to four equivalent Ho and four equivalent Cd atoms. In the thirteenth Cd site, Cd is bonded in a 11-coordinate geometry to four Ho and seven Cd atoms. In the fourteenth Cd site, Cd is bonded in a 11-coordinate geometry to four Ho and seven Cd atoms. There are one shorter (3.26 Å) and three longer (3.45 Å) Cd–Ho bond lengths. There are a spread of Cd–Cd bond distances ranging from 3.06–3.24 Å.

36 MATERIALS SCIENCE↗

Pretreatment with Sodium Methyl Mercaptide Increases Carbohydrate Yield during Kraft Pulping

Kraft pulping is the predominant technology in the pulp and paper industry for removing lignin from wood carbohydrates to produce paper, board, packaging, tissue, and specialty cellulose. However, the kraft process is energy intensive and expensive, and its yield is limited by the degradation of carbohydrates. Pretreatment can increase carbohydrate yield by limiting degradation via primary peeling of reducing end groups. However, protection of galactoglucomannan (GGM), the primary hemicellulose component of softwood, is minimal when conventional pretreatments are used. Here, we investigated the effectiveness of sodium methyl mercaptide pretreatment on southern pine wood chips under a range of experimental conditions. We found that pretreatment of biomass with 4.38% sodium methyl mercaptide at pH 12 and 105 °C for 60 min provided small but significant increases in xylan and cellulose yields relative to control conditions, but preservation of GGM was minimal. Furthermore, to provide insight into molecular-scale details of primary peeling, pretreatment, and alkaline hydrolysis, we performed classical molecular dynamics (MD) simulations under selected process conditions and quantum mechanical (QM) calculations of selected reactions. MD simulations showed that C1 of the GGM reducing end is more readily accessible by HO – and CH 3 S – ions than in cellulose. The free energy barrier for peeling calculated with QM is lower for GGM than for cellulose, indicating increased susceptibility to peeling. In addition, we found that GGM may be more susceptible to internal chain cleavage than cellulose. Thus, even though reducing end groups may be protected initially through pretreatment, new unprotected reducing end groups may be generated through alkaline hydrolysis. Taken together, these findings show the promise of methyl mercaptide as a pretreatment technology for cellulose retention and also provide molecular insight for improving its effectiveness toward GGM.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of controlled disorder on the dipolar spin-ice state of Ho-based pyrochlores

Pyrochlore magnets of the form 𝑅 2 ⁢𝐵 2 ⁢O 7 , in which rare-earth ions on the 𝑅 site form a three-dimensional network of corner-sharing tetrahedra, provide a canonical setting for geometrical frustration. Ho-based pyrochlores host a dipolar spin-ice ground state, characterized by Ising moments constrained by the ice rules and elementary excitations analogous to magnetic monopoles. Here, in this work, we examine how controlled chemical disorder influences this state by introducing site mixing on the nonmagnetic 𝐵 site in two compounds. Ho 2⁢ GaSbO 7 contains only Ga 3+ /Sb 5+ charge disorder, whereas Ho 2 ⁢ScSbO 7 exhibits both charge and substantial size disorder arising from the large ionic-radius mismatch between Sc 3+ and Sb 5+ . Although both materials retain the pyrochlore structure, neutron-scattering measurements reveal a reduced correlation length for the 𝑅/𝐵-site cation ordering and enhanced local structural distortions in Ho 2 ⁢ScSbO 7 . Despite these structural differences, bulk thermodynamic measurements and magnetic diffuse scattering demonstrate that both systems exhibit the defining signatures of a dipolar spin-ice state. Low-energy inelastic neutron spectroscopy further uncovers broad magnetic excitations that develop within the dipolar spin-ice regime, a feature absent in pristine Ho pyrochlores and indicative of disorder-induced splitting of the non-Kramers ground-state doublet. Together, these results show that controlled disorder generates tunable transverse-field-driven quantum fluctuations in Ho-based pyrochlores, although the dipolar spin-ice state is remarkably robust to this disorder.

magnetic anisotropy↗

Materials Data on Ho2NiAs2 by Materials Project

Ho2NiAs2 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Ho is bonded in a 9-coordinate geometry to three equivalent Ni and six As atoms. All Ho–Ni bond lengths are 3.02 Å. There are three shorter (2.89 Å) and three longer (3.02 Å) Ho–As bond lengths. Ni is bonded in a 3-coordinate geometry to six equivalent Ho and three equivalent As atoms. All Ni–As bond lengths are 2.37 Å. There are two inequivalent As sites. In the first As site, As is bonded in a 3-coordinate geometry to six equivalent Ho and three equivalent Ni atoms. In the second As site, As is bonded to six equivalent Ho atoms to form edge-sharing AsHo6 octahedra.

36 MATERIALS SCIENCE↗

In Situ High-Temperature Structural Analysis of High-Entropy Rare-Earth Sesquioxides

High-entropy rare-earth (RE) sesquioxides (RE 2 O 3 ) containing five cations in equimolar amounts have been investigated for a variety of applications, but little is known about their polymorphic behavior and coefficient of thermal expansion. Here, in this work, we evaluate the effect of the average ionic radius (AIR) on the polymorphism of high-entropy RE 2 O 3 . Powder samples of compositions 1 (Lu,Y,Ho,Nd,La) 2 O 3 (AIR = 0.938 Å) and 2 (Gd,Eu,Sm,Nd,La) 2 O 3 (AIR = 0.982 Å) were synthesized via a wet chemical method, and bead samples were prepared for aerodynamic levitation by melting the powders in a copper hearth. Structural transitions were monitored upon cooling from the melt to 1000 °C via in situ X-ray diffraction on aerodynamically levitated samples. The phase evolution was liquid, hexagonal H-type, and monoclinic B-type for composition 1 and liquid, cubic X-type, H-type, and B-type for composition 2. Based on their AIR, the general polymorphic transformations of the high-entropy RE 2 O 3 follow the trend of single-RE RE 2 O 3 , but the transition temperatures differ from those of single-RE RE 2 O 3 . The coefficient of thermal expansion values of the B-type phase of compositions 1 and 2 are similar to those of Gd 2 O 3 and previously published high-entropy RE 2 O 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Materials Data on Ho5Mg24 by Materials Project

Mg24Ho5 is alpha-derived structured and crystallizes in the cubic I-43m space group. The structure is three-dimensional. there are two inequivalent Mg sites. In the first Mg site, Mg is bonded in a 2-coordinate geometry to eleven Mg and two equivalent Ho atoms. There are a spread of Mg–Mg bond distances ranging from 2.99–3.38 Å. There are one shorter (3.22 Å) and one longer (3.71 Å) Mg–Ho bond lengths. In the second Mg site, Mg is bonded in a 12-coordinate geometry to eight Mg and four Ho atoms. There are one shorter (2.85 Å) and two longer (3.05 Å) Mg–Mg bond lengths. There are a spread of Mg–Ho bond distances ranging from 3.44–3.62 Å. There are two inequivalent Ho sites. In the first Ho site, Ho is bonded in a 12-coordinate geometry to twelve equivalent Mg and four equivalent Ho atoms. All Ho–Ho bond lengths are 3.60 Å. In the second Ho site, Ho is bonded in a 3-coordinate geometry to fifteen Mg and one Ho atom.

36 MATERIALS SCIENCE↗

Tuning the melting point and phase stability of rare-earth oxides to facilitate their crystal growth from the melt

The challenge of growing rare-earth (RE) sesquioxide crystals can be overcome by tailoring their structural stability and melting point via composition engineering. This work contributes to the advancement of the field of crystal growth of high-entropy oxides. A compound with only small REs (Lu,Y,Ho,Yb,Er) 2 O 3 maintains a cubic C-type structure upon cooling from the melt, as observed via in-situ high-temperature neutron diffraction on aerodynamically levitated samples. On the other hand, a compound with a mixture of small and large REs (Lu,Y,Ho,Nd,La) 2 O 3 crystallizes as a mixture of a primary C-type phase with an unstable secondary phase. Crystals of compositions (Lu,Y,Ho,Nd,La) 2 O 3 and (Lu,Y,Gd,Nd,La) 2 O 3 were grown by the micro-pulling-down (mPD) method with a single monoclinic B-type phase, while a powder of (Lu,Y,Ho,Yb,Er) 2 O 3 did not melt at the maximum operating temperature of an iridium-rhenium crucible. The minimization of the melting point of the two grown crystals is attributed to the mismatch in cation sizes. The electron probe microanalysis reveals that the general element segregation behavior in the crystals depends on the composition.

36 MATERIALS SCIENCE↗