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At least 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Materials Data on Cs2Ca(Cl2O)2 by Materials Project

Cs2Ca(OCl2)2 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. Cs is bonded in a 9-coordinate geometry to two equivalent O and seven Cl atoms. There are one shorter (3.26 Å) and one longer (3.51 Å) Cs–O bond lengths. There are a spread of Cs–Cl bond distances ranging from 3.45–3.97 Å. Ca is bonded in an octahedral geometry to two equivalent O and four Cl atoms. Both Ca–O bond lengths are 2.32 Å. There are two shorter (2.72 Å) and two longer (2.90 Å) Ca–Cl bond lengths. O is bonded in a distorted bent 120 degrees geometry to two equivalent Cs, one Ca, and one Cl atom. The O–Cl bond length is 1.67 Å. There are two inequivalent Cl sites. In the first Cl site, Cl is bonded in a 2-coordinate geometry to three equivalent Cs, one Ca, and one O atom. In the second Cl site, Cl is bonded in a 5-coordinate geometry to four equivalent Cs and one Ca atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on KNd(ClO)4 by Materials Project

KNd(OCl)4 crystallizes in the orthorhombic P2_12_12 space group. The structure is three-dimensional. K is bonded in a 6-coordinate geometry to two equivalent O and four equivalent Cl atoms. Both K–O bond lengths are 3.30 Å. There are two shorter (3.04 Å) and two longer (3.63 Å) K–Cl bond lengths. Nd is bonded in a 6-coordinate geometry to two equivalent O and four Cl atoms. Both Nd–O bond lengths are 2.37 Å. There are two shorter (2.71 Å) and two longer (2.95 Å) Nd–Cl bond lengths. There are two inequivalent O sites. In the first O site, O is bonded in a distorted bent 120 degrees geometry to one K and one O atom. The O–O bond length is 1.24 Å. In the second O site, O is bonded in a water-like geometry to one Nd and one Cl atom. The O–Cl bond length is 1.68 Å. There are two inequivalent Cl sites. In the first Cl site, Cl is bonded in a distorted water-like geometry to one Nd and one O atom. In the second Cl site, Cl is bonded in a distorted trigonal planar geometry to two equivalent K and one Nd atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Ga6CuSb7(TeCl3)8 by Materials Project

CuGa6Sb7(TeCl3)8 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. Cu1+ is bonded in a linear geometry to two equivalent Cl1- atoms. Both Cu–Cl bond lengths are 2.16 Å. There are three inequivalent Ga3+ sites. In the first Ga3+ site, Ga3+ is bonded in a tetrahedral geometry to four Cl1- atoms. There are a spread of Ga–Cl bond distances ranging from 2.17–2.29 Å. In the second Ga3+ site, Ga3+ is bonded in a tetrahedral geometry to four Cl1- atoms. There are a spread of Ga–Cl bond distances ranging from 2.19–2.22 Å. In the third Ga3+ site, Ga3+ is bonded in a tetrahedral geometry to four Cl1- atoms. There are a spread of Ga–Cl bond distances ranging from 2.20–2.23 Å. There are four inequivalent Sb3+ sites. In the first Sb3+ site, Sb3+ is bonded in an octahedral geometry to six Te2- atoms. There are a spread of Sb–Te bond distances ranging from 3.05–3.07 Å. In the second Sb3+ site, Sb3+ is bonded in a rectangular see-saw-like geometry to three Te2- and one Cl1- atom. There are one shorter (2.88 Å) and two longer (2.92 Å) Sb–Te bond lengths. The Sb–Cl bond length is 3.20 Å. In the third Sb3+ site, Sb3+ is bonded in a 6-coordinate geometry to three Te2- and three Cl1- atoms. There are a spread of Sb–Te bond distances ranging from 2.89–2.92 Å. There are a spread of Sb–Cl bond distances ranging from 3.25–3.38 Å. In the fourth Sb3+ site, Sb3+ is bonded in a distorted rectangular see-saw-like geometry to three Te2- and one Cl1- atom. There are a spread of Sb–Te bond distances ranging from 2.89–2.95 Å. The Sb–Cl bond length is 3.25 Å. There are four inequivalent Te2- sites. In the first Te2- site, Te2- is bonded in a 4-coordinate geometry to three Sb3+ and five Cl1- atoms. There are a spread of Te–Cl bond distances ranging from 3.87–4.07 Å. In the second Te2- site, Te2- is bonded in a 8-coordinate geometry to three Sb3+ and five Cl1- atoms. There are a spread of Te–Cl bond distances ranging from 3.82–4.13 Å. In the third Te2- site, Te2- is bonded in a 7-coordinate geometry to three Sb3+ and four Cl1- atoms. There are a spread of Te–Cl bond distances ranging from 3.69–3.99 Å. In the fourth Te2- site, Te2- is bonded in a 9-coordinate geometry to three Sb3+ and six Cl1- atoms. There are a spread of Te–Cl bond distances ranging from 3.61–4.14 Å. There are twelve inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a water-like geometry to one Cu1+ and one Ga3+ atom. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+, one Sb3+, and two Te2- atoms. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ and one Te2- atom. In the fourth Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ and two equivalent Te2- atoms. In the fifth Cl1- site, Cl1- is bonded in a distorted single-bond geometry to one Ga3+, one Sb3+, and three Te2- atoms. In the sixth Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+, one Sb3+, and three Te2- atoms. In the seventh Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ and one Te2- atom. In the eighth Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ and one Te2- atom. In the ninth Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+, one Sb3+, and two Te2- atoms. In the tenth Cl1- site, Cl1- is bonded in a distorted single-bond geometry to one Ga3+, one Sb3+, and one Te2- atom. In the eleventh Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ and two equivalent Te2- atoms. In the twelfth Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ and two equivalent Te2- atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Crystallographic Snapshots of Pre- and Post-Lanthanide Halide Hydrolysis─Reaction Products Captured by the 4-Amino-1,2,4-triazole Ligand

Reactions of lanthanide(III) chloride salts with 4-amino-1,2,4-triazole (4-NH 2 -1,2,4-Triaz) in azole melts have led to the isolation of both hydrolysis and non-hydrolysis products in the same synthesis with the inclusion of a variety of ligands, anions, and water, allowing us to capture crystallographic snapshots of different forms and intermediate hydrolysis fragments. The structural studies reported here include anhydrous and hydrated nonhydrolyzed complexes which were isolated alongside hydrolysis products giving oxide/hydroxide lanthanide(III) dimers, tetramers, and ultimately hexamers. The compounds isolated include [Nd 2 Cl 6 (μ 2 -4-NH 2 -1,2,4-Triaz) 4 (4-NH 2 -1,2,4-Triaz) 2 ], [Ce 2 Cl 4 (μ 2 -Cl) 2 (μ 2 -4-NH 2 -1,2,4-Triaz) 4 ] n , [Ce 2 (µ 2 -Cl) 4 (µ 2 -OH) 2 (µ 2 -4-NH 2 -1,2,4-Triaz) 2 ] n , [Ln 4 Cl 4 (µ 2 -Cl) 4 (µ 3 -OH) 4 (µ 2 -4-NH 2 -1,2,4-Triaz) 4 ] n •2nH 2 O (Ln = Ce, Nd), and [Ce 6 Cl 6 (µ 6 -O 0.5 )(µ 3 -Cl 0.5 ) 4 (µ 3 -Cl 0.75 ) 3 (µ 3 -OH) 0.75 (µ 2 -4-NH 2 -1,2,4-Triaz) 12 ((OH 2 ) 0.25 ) 2 ] 2 [CeCl 6 ][Cl 9 ]•xH 2 O. In all complexes all lanthanide atoms are pairwise connected via one or more 4-NH2-1,2,4-Triaz ligands and sometimes additional Cl - anions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Deciphering Photochemical Reaction Pathways of Aqueous Tetrachloroauric Acid by X-ray Transient Absorption Spectroscopy

Photolysis reaction pathways of [Au(III)Cl 4 ] - in aqueous solution have been investigated by time-resolved X-ray absorption spectroscopy. Ultraviolet excitation directly breaks the Au-Cl bond in [Au(III)Cl 4 ] - to form [Au(II)Cl 3 ] - that becomes highly reactive within 79 ps. Disproportionation of [Au(II)Cl 3 ] - generates [Au(I)Cl 2 ] - , which is stable for ≤ 10 mu s. In contrast, intense near-infrared lasers photolyze water to generate hydrated electrons, which then reduce [Au(III)Cl 4 ] - to [Au(II)Cl 3 ] - at 5 ns. Hydrated electrons further induce a chain reaction from [Au(II)Cl 3 ] - to [Au(0)Cl] - by successively removing one Cl - . The zero-valency Au anions quickly polymerize and condense to form Au nanoparticles, which become the dominating product after 400 s. Here our results reveal that the condensation of zero-valency Au starts with dimerization of gold clusters coordinated with chloride ions rather than direct condensation of pristine Au atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Changing-look Active Galactic Nuclei from the Dark Energy Spectroscopic Instrument. I. Sample from the Early Data

Changing-look active galactic nuclei (CL AGNs) can be generally confirmed by the emergence (turn-on) or disappearance (turn-off) of broad emission lines (BELs), associated with a transient timescale (about 100 ~ 5000 days) that is much shorter than predicted by traditional accretion disk models. We carry out a systematic CL AGN search by crossmatching the spectra coming from the Dark Energy Spectroscopic Instrument and the Sloan Digital Sky Survey. Following previous studies, we identify CL AGNs based on Hα, Hβ, and Mg ii at z ≤ 0.75 and Mg ii, C iii], and C iv at z > 0.75. We present 56 CL AGNs based on visual inspection and three selection criteria, including 2 Hα, 34 Hβ, 9 Mg ii, 18 C iii], and 1 C iv CL AGN. Eight cases show simultaneous appearances/disappearances of two BELs. We also present 44 CL AGN candidates with significant flux variation of BELs, but remaining strong broad components. In the confirmed CL AGNs, 10 cases show additional CL candidate features for different lines. In this paper, we find: (1) a 24:32 ratio of turn-on to turn-off CL AGNs; (2) an upper-limit transition timescale ranging from 330 to 5762 days in the rest frame; and (3) the majority of CL AGNs follow the bluer-when-brighter trend. Our results greatly increase the current CL census (~30%) and would be conducive to exploring the underlying physical mechanism.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Materials Data on Bi2Se4Cl7 by Materials Project

Bi2Se4Cl7 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are four inequivalent Bi+3.50+ sites. In the first Bi+3.50+ site, Bi+3.50+ is bonded in a 7-coordinate geometry to seven Cl1- atoms. There are a spread of Bi–Cl bond distances ranging from 2.55–3.39 Å. In the second Bi+3.50+ site, Bi+3.50+ is bonded in a 6-coordinate geometry to seven Cl1- atoms. There are a spread of Bi–Cl bond distances ranging from 2.56–3.39 Å. In the third Bi+3.50+ site, Bi+3.50+ is bonded in a 7-coordinate geometry to seven Cl1- atoms. There are a spread of Bi–Cl bond distances ranging from 2.57–3.30 Å. In the fourth Bi+3.50+ site, Bi+3.50+ is bonded in a distorted octahedral geometry to six Cl1- atoms. There are a spread of Bi–Cl bond distances ranging from 2.57–3.13 Å. There are eight inequivalent Se sites. In the first Se site, Se is bonded in a 2-coordinate geometry to two Se and two Cl1- atoms. There are one shorter (2.35 Å) and one longer (2.37 Å) Se–Se bond lengths. There are one shorter (3.59 Å) and one longer (3.65 Å) Se–Cl bond lengths. In the second Se site, Se is bonded in a distorted T-shaped geometry to two Se and one Cl1- atom. There are one shorter (2.35 Å) and one longer (2.36 Å) Se–Se bond lengths. The Se–Cl bond length is 3.57 Å. In the third Se site, Se is bonded in a rectangular see-saw-like geometry to two Se and two Cl1- atoms. The Se–Se bond length is 2.35 Å. There are one shorter (3.13 Å) and one longer (3.32 Å) Se–Cl bond lengths. In the fourth Se site, Se is bonded in a distorted water-like geometry to two Se atoms. The Se–Se bond length is 2.36 Å. In the fifth Se site, Se is bonded in a 3-coordinate geometry to two Se and two Cl1- atoms. There are one shorter (3.54 Å) and one longer (3.66 Å) Se–Cl bond lengths. In the sixth Se site, Se is bonded in a 4-coordinate geometry to two Se and two Cl1- atoms. There are one shorter (2.36 Å) and one longer (2.37 Å) Se–Se bond lengths. There are one shorter (3.22 Å) and one longer (3.51 Å) Se–Cl bond lengths. In the seventh Se site, Se is bonded in a distorted L-shaped geometry to two Se atoms. In the eighth Se site, Se is bonded in a distorted T-shaped geometry to two Se and one Cl1- atom. The Se–Cl bond length is 3.45 Å. There are fourteen inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to two Bi+3.50+ and one Se atom. In the second Cl1- site, Cl1- is bonded in a distorted trigonal non-coplanar geometry to three Bi+3.50+ atoms. In the third Cl1- site, Cl1- is bonded in a 3-coordinate geometry to two Bi+3.50+ and one Se atom. In the fourth Cl1- site, Cl1- is bonded in a 2-coordinate geometry to two Bi+3.50+ and one Se atom. In the fifth Cl1- site, Cl1- is bonded in a single-bond geometry to one Bi+3.50+ and two Se atoms. In the sixth Cl1- site, Cl1- is bonded in a distorted single-bond geometry to two Bi+3.50+ atoms. In the seventh Cl1- site, Cl1- is bonded in a 2-coordinate geometry to three Bi+3.50+ atoms. In the eighth Cl1- site, Cl1- is bonded in a distorted water-like geometry to two Bi+3.50+ atoms. In the ninth Cl1- site, Cl1- is bonded in a bent 120 degrees geometry to two Bi+3.50+ atoms. In the tenth Cl1- site, Cl1- is bonded in a 1-coordinate geometry to two Bi+3.50+ and one Se atom. In the eleventh Cl1- site, Cl1- is bonded in a single-bond geometry to two Bi+3.50+ atoms. In the twelfth Cl1- site, Cl1- is bonded in a distorted water-like geometry to two Bi+3.50+ atoms. In the thirteenth Cl1- site, Cl1- is bonded in a single-bond geometry to one Bi+3.50+ and two Se atoms. In the fourteenth Cl1- site, Cl1- is bonded in a distorted single-bond geometry to one Bi+3.50+ and two Se atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on CsRb(MnCl3)2 by Materials Project

RbCsMn2Cl6 is (Cubic) Perovskite-derived structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. there are two inequivalent Cs1+ sites. In the first Cs1+ site, Cs1+ is bonded to twelve Cl1- atoms to form CsCl12 cuboctahedra that share corners with two equivalent RbCl12 cuboctahedra, corners with four equivalent CsCl12 cuboctahedra, corners with six MnCl6 octahedra, faces with four CsCl12 cuboctahedra, faces with four equivalent RbCl12 cuboctahedra, and faces with six MnCl6 octahedra. The corner-sharing octahedral tilt angles are 14°. There are a spread of Cs–Cl bond distances ranging from 3.67–3.78 Å. In the second Cs1+ site, Cs1+ is bonded to twelve Cl1- atoms to form CsCl12 cuboctahedra that share corners with twelve equivalent RbCl12 cuboctahedra, faces with six equivalent CsCl12 cuboctahedra, and faces with eight MnCl6 octahedra. There are six shorter (3.70 Å) and six longer (3.72 Å) Cs–Cl bond lengths. There are two inequivalent Rb1+ sites. In the first Rb1+ site, Rb1+ is bonded to twelve Cl1- atoms to form RbCl12 cuboctahedra that share corners with six equivalent CsCl12 cuboctahedra, corners with six equivalent MnCl6 octahedra, faces with eight RbCl12 cuboctahedra, and faces with six equivalent MnCl6 octahedra. The corner-sharing octahedral tilt angles are 14°. There are six shorter (3.63 Å) and six longer (3.76 Å) Rb–Cl bond lengths. In the second Rb1+ site, Rb1+ is bonded to twelve Cl1- atoms to form RbCl12 cuboctahedra that share corners with four equivalent CsCl12 cuboctahedra, corners with eight equivalent RbCl12 cuboctahedra, faces with two equivalent RbCl12 cuboctahedra, faces with four equivalent CsCl12 cuboctahedra, and faces with eight MnCl6 octahedra. There are a spread of Rb–Cl bond distances ranging from 3.64–3.69 Å. There are two inequivalent Mn2+ sites. In the first Mn2+ site, Mn2+ is bonded to six Cl1- atoms to form MnCl6 octahedra that share a cornercorner with one RbCl12 cuboctahedra, corners with two equivalent CsCl12 cuboctahedra, corners with three MnCl6 octahedra, faces with three CsCl12 cuboctahedra, faces with four RbCl12 cuboctahedra, and a faceface with one MnCl6 octahedra. The corner-sharing octahedral tilt angles are 1°. There are a spread of Mn–Cl bond distances ranging from 2.54–2.56 Å. In the second Mn2+ site, Mn2+ is bonded to six Cl1- atoms to form MnCl6 octahedra that share corners with three equivalent CsCl12 cuboctahedra, corners with three equivalent MnCl6 octahedra, faces with three equivalent RbCl12 cuboctahedra, faces with four CsCl12 cuboctahedra, and a faceface with one MnCl6 octahedra. The corner-sharing octahedral tilt angles are 1°. All Mn–Cl bond lengths are 2.55 Å. There are seven inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a 6-coordinate geometry to two equivalent Cs1+, two equivalent Rb1+, and two equivalent Mn2+ atoms. In the second Cl1- site, Cl1- is bonded in a distorted linear geometry to one Cs1+, three Rb1+, and two equivalent Mn2+ atoms. The Cl–Cs bond length is 3.70 Å. In the third Cl1- site, Cl1- is bonded in a 6-coordinate geometry to three Cs1+, one Rb1+, and two equivalent Mn2+ atoms. In the fourth Cl1- site, Cl1- is bonded in a distorted linear geometry to one Cs1+, three Rb1+, and two equivalent Mn2+ atoms. Both Cl–Rb bond lengths are 3.69 Å. Both Cl–Mn bond lengths are 2.54 Å. In the fifth Cl1- site, Cl1- is bonded in a distorted linear geometry to three Cs1+, one Rb1+, and two Mn2+ atoms. In the sixth Cl1- site, Cl1- is bonded in a 6-coordinate geometry to four Rb1+ and two equivalent Mn2+ atoms. In the seventh Cl1- site, Cl1- is bonded in a distorted linear geometry to one Cs1+, three Rb1+, and two equivalent Mn2+ atoms. Both Cl–Mn bond lengths are 2.54 Å.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on P4N3Cl11 by Materials Project

P4N3Cl11 crystallizes in the monoclinic P2/c space group. The structure is three-dimensional. there are four inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to two N3- and two Cl1- atoms to form corner-sharing PN2Cl2 tetrahedra. Both P–N bond lengths are 1.58 Å. There are one shorter (2.00 Å) and one longer (2.02 Å) P–Cl bond lengths. In the second P5+ site, P5+ is bonded to one N3- and three Cl1- atoms to form corner-sharing PNCl3 tetrahedra. The P–N bond length is 1.57 Å. There are one shorter (2.00 Å) and two longer (2.01 Å) P–Cl bond lengths. In the third P5+ site, P5+ is bonded to one N3- and three Cl1- atoms to form corner-sharing PNCl3 tetrahedra. The P–N bond length is 1.56 Å. There are one shorter (2.00 Å) and two longer (2.01 Å) P–Cl bond lengths. In the fourth P5+ site, P5+ is bonded to two N3- and two Cl1- atoms to form corner-sharing PN2Cl2 tetrahedra. Both P–N bond lengths are 1.58 Å. There are one shorter (2.00 Å) and one longer (2.03 Å) P–Cl bond lengths. There are three inequivalent N3- sites. In the first N3- site, N3- is bonded in a bent 150 degrees geometry to two P5+ atoms. In the second N3- site, N3- is bonded in a bent 150 degrees geometry to two P5+ atoms. In the third N3- site, N3- is bonded in a distorted bent 150 degrees geometry to two P5+ atoms. There are eleven inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ and one Cl1- atom. The Cl–Cl bond length is 3.16 Å. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ atom. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ and one Cl1- atom. The Cl–Cl bond length is 3.55 Å. In the fourth Cl1- site, Cl1- is bonded in a 7-coordinate geometry to seven Cl1- atoms. There are a spread of Cl–Cl bond distances ranging from 3.11–3.35 Å. In the fifth Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ atom. In the sixth Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ atom. In the seventh Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ and one Cl1- atom. In the eighth Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ and one Cl1- atom. In the ninth Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ and one Cl1- atom. In the tenth Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ and one Cl1- atom. In the eleventh Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ and one Cl1- atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Fe5Te6(ClO9)2 by Materials Project

Fe5(TeO3)6Cl2 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are three inequivalent Fe+2.80+ sites. In the first Fe+2.80+ site, Fe+2.80+ is bonded to six O2- atoms to form edge-sharing FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 1.99–2.06 Å. In the second Fe+2.80+ site, Fe+2.80+ is bonded to six O2- atoms to form a mixture of distorted edge and corner-sharing FeO6 octahedra. The corner-sharing octahedra tilt angles range from 49–57°. There are a spread of Fe–O bond distances ranging from 2.03–2.54 Å. In the third Fe+2.80+ site, Fe+2.80+ is bonded to six O2- atoms to form corner-sharing FeO6 octahedra. The corner-sharing octahedra tilt angles range from 49–57°. There are a spread of Fe–O bond distances ranging from 1.97–2.11 Å. There are three inequivalent Te4+ sites. In the first Te4+ site, Te4+ is bonded in a 4-coordinate geometry to four O2- and two equivalent Cl1- atoms. There are a spread of Te–O bond distances ranging from 1.92–2.47 Å. There are one shorter (3.27 Å) and one longer (3.35 Å) Te–Cl bond lengths. In the second Te4+ site, Te4+ is bonded in a 5-coordinate geometry to five O2- and one Cl1- atom. There are a spread of Te–O bond distances ranging from 1.91–2.61 Å. The Te–Cl bond length is 3.33 Å. In the third Te4+ site, Te4+ is bonded in a 3-coordinate geometry to three O2- and three equivalent Cl1- atoms. There is two shorter (1.91 Å) and one longer (1.95 Å) Te–O bond length. There are a spread of Te–Cl bond distances ranging from 3.01–3.41 Å. There are nine inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal planar geometry to two Fe+2.80+, one Te4+, and one Cl1- atom. The O–Cl bond length is 3.42 Å. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to two Fe+2.80+ and one Te4+ atom. In the third O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Fe+2.80+, one Te4+, and one Cl1- atom. The O–Cl bond length is 3.31 Å. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to one Fe+2.80+ and two equivalent Te4+ atoms. In the fifth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Fe+2.80+ and one Te4+ atom. In the sixth O2- site, O2- is bonded in a 2-coordinate geometry to one Fe+2.80+, two Te4+, and one Cl1- atom. The O–Cl bond length is 3.32 Å. In the seventh O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Fe+2.80+, one Te4+, and one Cl1- atom. The O–Cl bond length is 3.30 Å. In the eighth O2- site, O2- is bonded in a 2-coordinate geometry to one Fe+2.80+, two Te4+, and two equivalent Cl1- atoms. There are one shorter (3.24 Å) and one longer (3.57 Å) O–Cl bond lengths. In the ninth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Fe+2.80+ and one Te4+ atom. Cl1- is bonded in a 6-coordinate geometry to six Te4+, six O2-, and two equivalent Cl1- atoms. There are one shorter (3.55 Å) and one longer (3.79 Å) Cl–Cl bond lengths.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on KH18OsN6(ClO2)4 by Materials Project

KH(O2Cl)4OsN6H15H2 crystallizes in the triclinic P1 space group. The structure is two-dimensional and consists of one hydrogen molecule; one OsN6H15 cluster; and one KH(O2Cl)4 sheet oriented in the (0, 0, 1) direction. In the OsN6H15 cluster, Os3+ is bonded in an octahedral geometry to six N+0.33- atoms. There are a spread of Os–N bond distances ranging from 1.89–2.22 Å. There are six inequivalent N+0.33- sites. In the first N+0.33- site, N+0.33- is bonded in a distorted trigonal planar geometry to one Os3+ and two H1+ atoms. Both N–H bond lengths are 1.03 Å. In the second N+0.33- site, N+0.33- is bonded in a distorted trigonal planar geometry to one Os3+ and two H1+ atoms. There is one shorter (1.02 Å) and one longer (1.03 Å) N–H bond length. In the third N+0.33- site, N+0.33- is bonded in a distorted trigonal planar geometry to one Os3+ and two H1+ atoms. There is one shorter (1.02 Å) and one longer (1.03 Å) N–H bond length. In the fourth N+0.33- site, N+0.33- is bonded in a trigonal non-coplanar geometry to one Os3+ and three H1+ atoms. There is one shorter (1.02 Å) and two longer (1.03 Å) N–H bond length. In the fifth N+0.33- site, N+0.33- is bonded in a distorted trigonal non-coplanar geometry to one Os3+ and three H1+ atoms. All N–H bond lengths are 1.03 Å. In the sixth N+0.33- site, N+0.33- is bonded in a trigonal non-coplanar geometry to one Os3+ and three H1+ atoms. There is one shorter (1.02 Å) and two longer (1.03 Å) N–H bond length. There are fifteen inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one N+0.33- atom. In the second H1+ site, H1+ is bonded in a single-bond geometry to one N+0.33- atom. In the third H1+ site, H1+ is bonded in a single-bond geometry to one N+0.33- atom. In the fourth H1+ site, H1+ is bonded in a single-bond geometry to one N+0.33- atom. In the fifth H1+ site, H1+ is bonded in a single-bond geometry to one N+0.33- atom. In the sixth H1+ site, H1+ is bonded in a single-bond geometry to one N+0.33- atom. In the seventh H1+ site, H1+ is bonded in a single-bond geometry to one N+0.33- atom. In the eighth H1+ site, H1+ is bonded in a single-bond geometry to one N+0.33- atom. In the ninth H1+ site, H1+ is bonded in a single-bond geometry to one N+0.33- atom. In the tenth H1+ site, H1+ is bonded in a single-bond geometry to one N+0.33- atom. In the eleventh H1+ site, H1+ is bonded in a single-bond geometry to one N+0.33- atom. In the twelfth H1+ site, H1+ is bonded in a single-bond geometry to one N+0.33- atom. In the thirteenth H1+ site, H1+ is bonded in a single-bond geometry to one N+0.33- atom. In the fourteenth H1+ site, H1+ is bonded in a single-bond geometry to one N+0.33- atom. In the fifteenth H1+ site, H1+ is bonded in a single-bond geometry to one N+0.33- atom. In the KH(O2Cl)4 sheet, K1+ is bonded in a 8-coordinate geometry to six O2- and two Cl1- atoms. There are a spread of K–O bond distances ranging from 2.87–3.43 Å. There are one shorter (3.16 Å) and one longer (3.25 Å) K–Cl bond lengths. H1+ is bonded in a single-bond geometry to one Cl1- atom. The H–Cl bond length is 1.30 Å. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one K1+ and one Cl1- atom. The O–Cl bond length is 1.48 Å. In the second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one K1+ and one Cl1- atom. The O–Cl bond length is 1.47 Å. In the third O2- site, O2- is bonded in a single-bond geometry to one K1+ and one Cl1- atom. The O–Cl bond length is 1.47 Å. In the fourth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one Cl1- atom. The O–Cl bond length is 1.46 Å. In the fifth O2- site, O2- is bonded in a single-bond geometry to one K1+ and one Cl1- atom. The O–Cl bond length is 1.45 Å. In the sixth O2- site, O2- is bonded in a single-bond geometry to one Cl1- atom. The O–Cl bond length is 1.45 Å. In the seventh O2- site, O2- is bonded in a single-bond geometry to one Cl1- atom. The O–Cl bond length is 1.49 Å. In the eighth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one K1+ and one Cl1- atom. The O–Cl bond length is 1.47 Å. There are four inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a tetrahedral geometry to four O2- atoms. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one K1+ atom. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one K1+ and one H1+ atom. In the fourth Cl1- site, Cl1- is bonded in a tetrahedral geometry to four O2- atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Ca12Al11Si3Cl5O32 by Materials Project

Ca12Al11Si3O32Cl5 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are twelve inequivalent Ca2+ sites. In the first Ca2+ site, Ca2+ is bonded to six O2- and one Cl1- atom to form distorted CaClO6 pentagonal bipyramids that share a cornercorner with one CaClO6 pentagonal bipyramid, corners with four AlO4 tetrahedra, edges with three CaClO6 pentagonal bipyramids, an edgeedge with one SiO4 tetrahedra, and edges with two AlO4 tetrahedra. There are a spread of Ca–O bond distances ranging from 2.34–2.64 Å. The Ca–Cl bond length is 2.77 Å. In the second Ca2+ site, Ca2+ is bonded to six O2- and one Cl1- atom to form distorted CaClO6 pentagonal bipyramids that share a cornercorner with one CaClO6 pentagonal bipyramid, corners with two AlO4 tetrahedra, corners with two SiO4 tetrahedra, edges with four CaClO6 pentagonal bipyramids, and edges with three AlO4 tetrahedra. There are a spread of Ca–O bond distances ranging from 2.40–2.51 Å. The Ca–Cl bond length is 2.81 Å. In the third Ca2+ site, Ca2+ is bonded to six O2- and one Cl1- atom to form distorted CaClO6 pentagonal bipyramids that share a cornercorner with one CaClO6 pentagonal bipyramid, a cornercorner with one SiO4 tetrahedra, corners with three AlO4 tetrahedra, edges with three CaClO6 pentagonal bipyramids, an edgeedge with one SiO4 tetrahedra, and edges with two AlO4 tetrahedra. There are a spread of Ca–O bond distances ranging from 2.38–2.62 Å. The Ca–Cl bond length is 2.76 Å. In the fourth Ca2+ site, Ca2+ is bonded to six O2- and one Cl1- atom to form distorted CaClO6 pentagonal bipyramids that share a cornercorner with one CaClO6 pentagonal bipyramid, a cornercorner with one SiO4 tetrahedra, corners with three AlO4 tetrahedra, edges with four CaClO6 pentagonal bipyramids, and edges with three AlO4 tetrahedra. There are a spread of Ca–O bond distances ranging from 2.37–2.54 Å. The Ca–Cl bond length is 2.82 Å. In the fifth Ca2+ site, Ca2+ is bonded to six O2- and one Cl1- atom to form distorted CaClO6 pentagonal bipyramids that share a cornercorner with one CaClO6 pentagonal bipyramid, a cornercorner with one SiO4 tetrahedra, corners with three AlO4 tetrahedra, edges with three CaClO6 pentagonal bipyramids, and edges with three AlO4 tetrahedra. There are a spread of Ca–O bond distances ranging from 2.37–2.53 Å. The Ca–Cl bond length is 2.81 Å. In the sixth Ca2+ site, Ca2+ is bonded to six O2- and one Cl1- atom to form distorted CaClO6 pentagonal bipyramids that share a cornercorner with one CaClO6 pentagonal bipyramid, a cornercorner with one SiO4 tetrahedra, corners with three AlO4 tetrahedra, edges with three CaClO6 pentagonal bipyramids, an edgeedge with one SiO4 tetrahedra, and edges with two AlO4 tetrahedra. There are a spread of Ca–O bond distances ranging from 2.35–2.57 Å. The Ca–Cl bond length is 2.76 Å. In the seventh Ca2+ site, Ca2+ is bonded in a distorted hexagonal planar geometry to six O2- atoms. There are a spread of Ca–O bond distances ranging from 2.33–2.56 Å. In the eighth Ca2+ site, Ca2+ is bonded to six O2- and one Cl1- atom to form distorted CaClO6 pentagonal bipyramids that share a cornercorner with one CaClO6 pentagonal bipyramid, a cornercorner with one SiO4 tetrahedra, corners with three AlO4 tetrahedra, edges with three CaClO6 pentagonal bipyramids, an edgeedge with one SiO4 tetrahedra, and edges with two AlO4 tetrahedra. There are a spread of Ca–O bond distances ranging from 2.39–2.60 Å. The Ca–Cl bond length is 2.76 Å. In the ninth Ca2+ site, Ca2+ is bonded to six O2- and one Cl1- atom to form distorted CaClO6 pentagonal bipyramids that share a cornercorner with one CaClO6 pentagonal bipyramid, corners with four AlO4 tetrahedra, edges with three CaClO6 pentagonal bipyramids, an edgeedge with one SiO4 tetrahedra, and edges with two AlO4 tetrahedra. There are a spread of Ca–O bond distances ranging from 2.35–2.60 Å. The Ca–Cl bond length is 2.76 Å. In the tenth Ca2+ site, Ca2+ is bonded to six O2- and one Cl1- atom to form distorted CaClO6 pentagonal bipyramids that share a cornercorner with one CaClO6 pentagonal bipyramid, a cornercorner with one SiO4 tetrahedra, corners with three AlO4 tetrahedra, edges with three CaClO6 pentagonal bipyramids, an edgeedge with one SiO4 tetrahedra, and edges with two AlO4 tetrahedra. There are a spread of Ca–O bond distances ranging from 2.35–2.55 Å. The Ca–Cl bond length is 2.75 Å. In the eleventh Ca2+ site, Ca2+ is bonded to six O2- and one Cl1- atom to form distorted CaClO6 pentagonal bipyramids that share a cornercorner with one CaClO6 pentagonal bipyramid, a cornercorner with one SiO4 tetrahedra, corners with three AlO4 tetrahedra, edges with three CaClO6 pentagonal bipyramids, and edges with three AlO4 tetrahedra. There are a spread of Ca–O bond distances ranging from 2.40–2.64 Å. The Ca–Cl bond length is 2.80 Å. In the twelfth Ca2+ site, Ca2+ is bonded in a distorted hexagonal planar geometry to six O2- atoms. There are a spread of Ca–O bond distances ranging from 2.33–2.50 Å. There are eleven inequivalent Al3+ sites. In the first Al3+ site, Al3+ is bonded to four O2- atoms to form AlO4 tetrahedra that share corners with three CaClO6 pentagonal bipyramids, a cornercorner with one SiO4 tetrahedra, corners with three AlO4 tetrahedra, and edges with two CaClO6 pentagonal bipyramids. There are a spread of Al–O bond distances ranging from 1.75–1.80 Å. In the second Al3+ site, Al3+ is bonded to four O2- atoms to form AlO4 tetrahedra that share corners with two CaClO6 pentagonal bipyramids, corners with three AlO4 tetrahedra, and edges with three CaClO6 pentagonal bipyramids. There is one shorter (1.75 Å) and three longer (1.79 Å) Al–O bond length. In the third Al3+ site, Al3+ is bonded to four O2- atoms to form AlO4 tetrahedra that share corners with three CaClO6 pentagonal bipyramids, corners with two AlO4 tetrahedra, corners with two SiO4 tetrahedra, and edges with two CaClO6 pentagonal bipyramids. There are a spread of Al–O bond distances ranging from 1.74–1.80 Å. In the fourth Al3+ site, Al3+ is bonded to four O2- atoms to form AlO4 tetrahedra that share corners with three CaClO6 pentagonal bipyramids, corners with two AlO4 tetrahedra, corners with two SiO4 tetrahedra, and edges with two CaClO6 pentagonal bipyramids. There are a spread of Al–O bond distances ranging from 1.74–1.79 Å. In the fifth Al3+ site, Al3+ is bonded to four O2- atoms to form AlO4 tetrahedra that share corners with two CaClO6 pentagonal bipyramids, corners with three AlO4 tetrahedra, and edges with three CaClO6 pentagonal bipyramids. There are a spread of Al–O bond distances ranging from 1.74–1.80 Å. In the sixth Al3+ site, Al3+ is bonded to four O2- atoms to form AlO4 tetrahedra that share corners with two CaClO6 pentagonal bipyramids, corners with three AlO4 tetrahedra, and edges with three CaClO6 pentagonal bipyramids. There are a spread of Al–O bond distances ranging from 1.75–1.80 Å. In the seventh Al3+ site, Al3+ is bonded to four O2- atoms to form AlO4 tetrahedra that share corners with four CaClO6 pentagonal bipyramids, a cornercorner with one AlO4 tetrahedra, and corners with three SiO4 tetrahedra. There is one shorter (1.73 Å) and three longer (1.78 Å) Al–O bond length. In the eighth Al3+ site, Al3+ is bonded to four O2- atoms to form AlO4 tetrahedra that share corners with three CaClO6 pentagonal bipyramids, a cornercorner with one SiO4 tetrahedra, corners with three AlO4 tetrahedra, and edges with two CaClO6 pentagonal bipyramids. There is three shorter (1.75 Å) and one longer (1.80 Å) Al–O bond length. In the ninth Al3+ site, Al3+ is bonded to four O2- atoms to form AlO4 tetrahedra that share corners with three CaClO6 pentagonal bipyramids, corners with three AlO4 tetrahedra, and edges with two CaClO6 pentagonal bipyramids. There are a spread of Al–O bond distances ranging from 1.73–1.80 Å. In the tenth Al3+ site, Al3+ is bonded to four O2- atoms to form AlO4 tetrahedra that share corners with four CaClO6 pentagonal bipyramids, corners with four AlO4 tetrahedra, and edges with two CaClO6 pentagonal bipyramids. All Al–O bond lengths are 1.77 Å. In the eleventh Al3+ site, Al3+ is bonded to four O2- atoms to form AlO4 tetrahedra that share corners with two CaClO6 pentagonal bipyramids, corners with three AlO4 tetrahedra, and edges with three CaClO6 pentagonal bipyramids. There are a spread of Al–O bond distances ranging from 1.75–1.80 Å. There are three inequivalent Si4+ sites. In the first Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share corners with three CaClO6 pentagonal bipyramids, corners with three AlO4 tetrahedra, and edges with two CaClO6 pentagonal bipyramids. There is one shorter (1.61 Å) and three longer (1.67 Å) Si–O bond length. In the second Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share corners with three CaClO6 pentagonal bipyramids, corners with three AlO4 tetrahedra, and edges with two CaClO6 pentagonal bipyramids. There are a spread of Si–O bond distances ranging from 1.61–1.68 Å. In the third Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share corners with three CaClO6 pentagonal bipyramids, corners with three AlO4 tetrahedra, and edges with two CaClO6 pentagonal bipyramids. There are a spread of Si–O bond distances ranging from 1.61–1.68 Å. There are thirty-two inequivalent O2- sites. In the first O2- site, O2- is bonded in a 4-coordinate geometry to two Ca2+ and two Al3+ atoms. In the second O2- site, O2- is bonded in a 4-coordinate geometry to two Ca2+ and two Al3+ atoms. In the third O2- site, O2- is bonded in a 4-coordinate geometry to two Ca2+, one Al3+, and one Si4+ atom. In the fourth O2- site, O2- is bonded in a 2-coordinate geometry to two Ca2+, one Al3+, and one Si4+ atom. In the fifth O2- site, O2- is bonded in a 4-coordinate geometry to two Ca2+ and two Al3+ atoms. In the sixth O2- site, O2- is bonded to two Ca2+ and two Al3+ atoms to form distorted corner-sharing OCa2Al2 trigonal pyramids. In the seventh O2- site, O2- is bonded in a 4-coordinate geometry to two Ca2+ and two Al3+ atoms. In the eighth O2- site, O2- is bonded in a 4-coordinate geometry to two Ca2+, one Al3+, and one Si4+ atom. In the ninth O2- site, O2- is bonded in a 4-coordinate geometry to two Ca2+ and two Al3+ atoms. In the tenth O2- site, O2- is bonded to three Ca2+ and one Al3+ atom to form distorted OCa3Al tetrahedra that share a cornercorner with one OCa3Al tetrahedra and corners with four OCa2Al2 trigonal pyramids. In the eleventh O2- site, O2- is bonded in a 4-coordinate geometry to two Ca2+, one Al3+, and one Si4+ atom. In the twelfth O2- site, O2- is bonded in a 2-coordinate geometry to two Ca2+, one Al3+, and one Si4+ atom. In the thirteenth O2- site, O2- is bonded in a 4-coordinate geometry to two Ca2+ and two Al3+ atoms. In the fourteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Ca2+ and two Al3+ atoms. In the fifteenth O2- site, O2- is bonded in a 1-coordinate geometry to three Ca2+ and one Si4+ atom. In the sixteenth O2- site, O2- is bonded to three Ca2+ and one Al3+ atom to form distorted OCa3Al tetrahedra that share corners with two OCa3Al tetrahedra and a cornercorner with one OCa2Al2 trigonal pyramid. In the seventeenth O2- site, O2- is bonded in a 1-coordinate geometry to three Ca2+ and one Si4+ atom. In the eighteenth O2- site, O2- is bonded in a 4-coordinate geometry to two Ca2+ and two Al3+ atoms. In the nineteenth O2- site, O2- is bonded in a 2-coordinate geometry to two Ca2+, one Al3+, and one Si4+ atom. In the twentieth O2- site, O2- is bonded in a 4-coordinate geometry to two Ca2+ and two Al3+ atoms. In the twenty-first O2- site, O2- is bonded to three Ca2+ and one Al3+ atom to form distorted OCa3Al tetrahedra that share a cornercorner with one OCa3Al tetrahedra, corners with two OCa2Al2 trigonal pyramids, and an edgeedge with one OCa2Al2 trigonal pyramid

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Cd2Ni(ClO2)6 by Materials Project

(CdCl2)2Ni(O3Cl)2(O2)3 crystallizes in the orthorhombic Fdd2 space group. The structure is one-dimensional and consists of twenty-four hydrogen peroxide molecules; eight Ni(O3Cl)2 clusters; and eight CdCl2 ribbons oriented in the (1, 0, 0) direction. In each Ni(O3Cl)2 cluster, Ni is bonded in a distorted trigonal pyramidal geometry to four O atoms. There are two shorter (1.82 Å) and two longer (2.23 Å) Ni–O bond lengths. There are three inequivalent O sites. In the first O site, O is bonded in a distorted bent 120 degrees geometry to one Ni and one Cl atom. The O–Cl bond length is 1.66 Å. In the second O site, O is bonded in a bent 120 degrees geometry to one Ni and one O atom. The O–O bond length is 1.24 Å. In the third O site, O is bonded in a single-bond geometry to one O atom. Cl is bonded in a single-bond geometry to one O atom. In each CdCl2 ribbon, Cd is bonded in a square co-planar geometry to four Cl atoms. There are two shorter (2.56 Å) and two longer (2.58 Å) Cd–Cl bond lengths. There are two inequivalent Cl sites. In the first Cl site, Cl is bonded in an L-shaped geometry to two equivalent Cd atoms. In the second Cl site, Cl is bonded in an L-shaped geometry to two equivalent Cd atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Origin of the isotopic composition of natural perchlorate: Experimental results for the impact of reaction pathway and initial ClO x reactant

Natural perchlorate (ClO 4 - ) exists in many places on Earth, in lunar regolith, meteorites, and on the surface of Mars. Terrestrial natural ClO 4 - has widely variable Cl and O stable isotopic compositions (δ 37 Cl, δ 18 O, Δ 17 O). The δ 18 O and Δ 17 O values of ClO 4 - from the most hyper-arid locations co-vary. ClO 4 - from less arid areas has relatively little 17 O excess and poor Δ 17 O-δ 18 O correlation. ClO 4 - from the Atacama Desert has unusually low δ 37 Cl (<-10‰) and exhibits a positive correlation between δ 37 Cl and δ 18 O, while the δ 37 Cl of ClO 4 - from all other locations varies between -5 and +7‰ with no δ 37 Cl-δ 18 O covariation. To evaluate the impact of different precursors (ClO x ) and reaction pathways on the isotopic composition of ClO 4 - , we measured the isotopic composition of ClO 4 - produced in the laboratory by UV or O 3 mediated aqueous oxidation of Cl-, OCl-, ClO2-, and ClO2° as well as O 3 mediated oxidation of dry NaCl. ClO x oxidation in aqueous or dry systems enriched in O 3 produced ClO 4 - with Δ 17 O values that generally increased with the number of O atoms required and included evidence that the site-specific 17 O anomaly in O 3 was preferentially transferred to ClO 4 - . Based on the inferred number of O atoms sourced from O 3 , and known Cl and O reaction pathways, it appears that ClO 2 ° and ClO 3 * were required intermediates in the production of ClO 4 - in the O 3 experiments. ClO x aqueous oxidation by UV irradiation produced ClO 4 - with a large range of δ 18 O values and little or no 17 O anomaly. ClO 3 - was produced to a much greater extent than ClO 4 - in all experiments except dry oxidation of NaCl by O 3 . The isotopic composition of ClO 3 - was distinct from that of ClO 4 - produced from the same initial reactants. Combined results of O 3 and UV mediated reactions largely bracketed the range of natural ClO 4 - δ 18 O and Δ 17 O values as well as δ 37 Cl values of non-Atacama natural samples, but no conditions produced the low δ 37 Cl values of Atacama ClO 4 - . Finally, our results indicate that variation in production mechanisms, possibly combined with isotopically variable precursors, could be responsible for much of the observed isotopic variation in natural ClO 4 - and ClO 3 - .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Exploring the Role of Neutral 4-Amino-1,2,4-triazole in the Formation of Hexanuclear f-Element Hydrolysis Products

Our recent observations of an unexpected Ce(III) hydrolysis product from the reaction of 4-amino-1,2,4-triazole (4-NH 2 -1,2,4-Triaz) with CeCl 3 ·7H 2 O, [Ce 6 (μ 3 -O) 4 (μ 3 -OH) 2 (μ 3 -Cl) 2 (Cl) 6 (μ 2 -4-NH 2 -1,2,4-Triaz) 12 ]·7H 2 O, the first high-nuclearity lanthanide complex where all Ln atoms are connected pairwise through 12 N-donor ligands or 12 neutral bridging ligands of any type, prompted us to explore the utility of this ligand in trapping additional f-element examples. Reactions of LnCl 3 ·6H 2 O (Ln = Nd, Eu, Ho) with a large excess of 4-NH 2 -1,2,4-Triaz (20 equiv) and with the addition of small amounts of water to help solubilize the metal salts led to the isolation of the unique hydrolysis products [Nd 6 (μ 3 -OH) 8 Cl 6 (μ 2 -4-NH 2 -1,2,4-Triaz) 12 ][Cl 4 ]·2H 2 O, [Eu 6 (μ 6 -Cl) 0.23 (μ 3 -O 0.77 ) 4 (μ 3 -O) 2.6 (μ 3 -Cl) 0.4 Cl 6 (μ 2 -4-NH 2 -1,2,4-Triaz) 12 ], and [Ho 6 (μ 6 -Cl) 0.21 (μ 3 -O 0.79 ) 4 (μ 3 -OH) 2 Cl 6 (μ 2 -4-NH 2 -1,2,4-Triaz) 12 ][Cl] 3.4 . Here, we also report a Ce(III) analogue prepared in glassware contaminated with Pb(OAc) 2 , namely, [Ce 6 (μ 3 -OH) 8 (BrPbBr 5 )(μ 2 -4-NH 2 -1,2,4-Triaz) 11.5 (OH 2 ) 6 ][Pb 0.84 Br 4.2 ][Br] 3.8 ·2(4-NH 2 -1,2,4-Triaz)·3.6H 2 O. The Nd(III) complex is the structurally most ordered with a clear [Nd 6 (μ 3 -OH) 8 ] cluster core, while the Eu(III) and Ho(III) compounds contain partial occupancy of a μ 6 position and thus result in an incomplete Ln 6 O 9 cluster core formation. The crystallographic results suggest that the 4-NH 2 -1,2,4-Triaz ligand brings Ln(III) ions together, followed by the formation of an Ln 6 O 8 or Ln 6 O 9 core with whatever remaining anions or ligands can be incorporated. Given the complexity of the hydrolysis products of nuclear waste, we expect to continue to find a myriad of closely related complex structures of these types for the f-elements.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Mechanistic Insights into Visible-Light-Induced ATRA Reactions Powered by the Symbiotic Relationship between Cu(II)/Cu(I) Phenanthroline Complexes

As photoredox catalysis continues to yield promising chemical transformations, there is an increased need to understand how specific photocatalysts function to improve reaction efficiencies while expanding their scope. Copper-phenanthroline-based photocatalysts such as Cu II (dap)Cl 2 (dap = 2,9-di(p-anisyl)-1,10-phenanthroline) and [Cu I (dap) 2 ]Cl were both found to be equally capable of olefin activation through electrophilic atom transfer radical addition (ATRA) reactions. Although these molecular catalysts have proven successful, many intermediates suggested in the proposed catalytic cycles have never been detected. One undetermined aspect in this chemistry is related to how one equivalent of Cu II (dap)Cl 2 generates half of an equivalent of [Cu I (dap) 2 ] + during the photocatalytic sequence. To this end, we initially used more synthetically accessible model systems, namely, [Cu I (dpp) 2 ]Cl and Cu II (dpp)Cl 2 (dpp = 2,9-diphenyl-1,10-phenanthroline), to glean detailed mechanistic insights into this unusual symbiotic relationship. We directly detected several intermediates involved in the ATRA photocatalytic cycle using these model chromophores in conjunction with electronic spectroscopy, infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) mass spectrometry, electronic structure calculations, EPR spin-trap experiments, and 1 H NMR spectroscopy. We found that the unique ligand lability and coordinating properties of acetonitrile enable both the in situ oxidation of [Cu I (dpp) 2 ] + by tosyl chloride into Cu II (dpp)Cl 2 and the visible-light-induced homolysis of the Cu II –Cl bond, which initiates the conversion to the Cu I species [Cu I (dpp) 2 ][Cu I Cl 2 ]. Here, the combined findings from the present study of the catalytic cycle demonstrate that the symbiotic relationship between Cu II (dpp)Cl 2 and [Cu I (dpp) 2 ] + , as well as between Cu II (dap)Cl 2 and [Cu I (dap) 2 ] + , is the critical factor enabling the ATRA photoreaction by departing from either photocatalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Enhanced Selectivity for C 2 H 4 Production from C 2 H 6 on Partially Chlorinated IrO 2 (110) Surfaces

Modifying metal oxide surfaces to limit their oxidizing activity can provide a means of improving catalytic selectivity toward the partial oxidation of light alkanes. Here, in this study, we investigated the oxidation of C 2 H 6 on Cl-modified IrO 2 (110) surfaces using temperature-programmed reaction spectroscopy (TPRS) and first-principles microkinetic modeling. We find that substituting Cl for O in the IrO 2 (110) surface enhances the selectivity for C 2 H 6 conversion to C 2 H 4 during TPRS by suppressing extensive oxidation to CO x products, while also either enhancing C 2 H 4 production or altering it to a lesser extent, depending on the initial C 2 H 6 coverage. The C 2 H 4 selectivity increased with increasing C 2 H 6 and Cl coverage, but reached a limiting value below 50%. The Cl coverage changed negligibly during C 2 H 6 oxidation, and the surface reactivity decreased only marginally for Cl coverages up to 0.5 ML (monolayer). TPRS simulations using a microkinetic model predict C 2 H 4 and CO x product yields as a function of the Cl coverage that agree closely with the experimental results. According to the simulations, C 2 H 6 conversion to C 2 H 4 occurs on Cl-IrO 2 (110) by the hydrogenation of C 2 H 3 * species adsorbed in blocked states, in which neighboring sites are occupied only by unreactive HO and Cl species. The microkinetic modeling shows that H-hopping away from surface HO groups provides a relatively efficient route for C 2 H 3 * to escape blocked configurations and dehydrogenate, and that this process can limit the C 2 H 4 selectivity on Cl-IrO 2 (110) under the conditions studied. Overall, our results demonstrate that Cl-substitution into IrO 2 (110) enhances the selectivity for C 2 H 4 production from C 2 H 6 and provides insights into the reaction mechanism that can guide strategies to further improve the C 2 H 4 selectivity.

IrO2↗
DOE OSTI2020

Materials Data on H7ClO7 by Materials Project

H7O3ClO4 crystallizes in the orthorhombic Pbca space group. The structure is zero-dimensional and consists of eight ClO4 clusters and eight H7O3 clusters. In each ClO4 cluster, there are four inequivalent O sites. In the first O site, O is bonded in a distorted single-bond geometry to one Cl atom. The O–Cl bond length is 1.49 Å. In the second O site, O is bonded in a single-bond geometry to one Cl atom. The O–Cl bond length is 1.45 Å. In the third O site, O is bonded in a single-bond geometry to one Cl atom. The O–Cl bond length is 1.47 Å. In the fourth O site, O is bonded in a single-bond geometry to one Cl atom. The O–Cl bond length is 1.45 Å. Cl is bonded in a tetrahedral geometry to four O atoms. In each H7O3 cluster, there are seven inequivalent H sites. In the first H site, H is bonded in a single-bond geometry to one O atom. The H–O bond length is 1.00 Å. In the second H site, H is bonded in a single-bond geometry to one O atom. The H–O bond length is 1.00 Å. In the third H site, H is bonded in a single-bond geometry to one O atom. The H–O bond length is 0.99 Å. In the fourth H site, H is bonded in a linear geometry to two O atoms. There is one shorter (1.04 Å) and one longer (1.52 Å) H–O bond length. In the fifth H site, H is bonded in a linear geometry to two O atoms. There is one shorter (1.06 Å) and one longer (1.46 Å) H–O bond length. In the sixth H site, H is bonded in a single-bond geometry to one O atom. The H–O bond length is 0.99 Å. In the seventh H site, H is bonded in a single-bond geometry to one O atom. The H–O bond length is 0.99 Å. There are three inequivalent O sites. In the first O site, O is bonded in a trigonal non-coplanar geometry to three H atoms. In the second O site, O is bonded in a trigonal non-coplanar geometry to three H atoms. In the third O site, O is bonded in a distorted trigonal non-coplanar geometry to three H atoms.

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