skip to main content


Title: Dibridged, Monobridged, Vinylidene-Like, and Linear Structures for the Alkaline Earth Dihydrides Be 2 H 2 , Mg 2 H 2 , Ca 2 H 2 , Sr 2 H 2 , and Ba 2 H 2 . Proposals for Observations
Award ID(s):
1664379
NSF-PAR ID:
10191087
Author(s) / Creator(s):
; ; ; ; ; ;
Date Published:
Journal Name:
Inorganic Chemistry
Volume:
59
Issue:
15
ISSN:
0020-1669
Page Range / eLocation ID:
10404 to 10408
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    We report the hydrothermal syntheses and crystal structures of aquabis(2,2′-bipyridine-κ 2 N , N ′)copper(II) hexafluoridosilicate tetrahydrate, [Cu(bpy) 2 (H 2 O)][SiF 6 ]·4H 2 O (bpy is 2,2′-bipyridine, C 10 H 8 N 2 ), (I), bis(2,2′-bipyridine-3κ 2 N , N ′)-di-μ-fluorido-1:3κ 2 F : F ;2:3κ 2 F : F -decafluorido-1κ 5 F ,2κ 5 F -ditantalum(V)copper(II), [Cu(bpy) 2 (TaF 6 ) 2 ], (II), tris(2,2′-bipyridine-κ 2 N , N ′)copper(II) bis[hexafluoridotantalate(V)], [Cu(bpy) 3 ][TaF 6 ] 2 , (III), and catena -poly[[diaqua(2,2′-bipyridine-κ 2 N , N ′)copper(II)]-μ-fluorido-tetrafluoridotin-μ-fluorido], [Cu(bpy)(H 2 O) 2 SnF 6 ] n , (IV). Compounds (I), (II) and (III) contain locally chiral copper coordination complexes with C 2 , D 2 , and D 3 symmetry, respectively. The extended structures of (I) and (IV) are consolidated by O—H...F and O—H...O hydrogen bonds. The structure of (III) was found to be a merohedral (racemic) twin. 
    more » « less
  2. Despite the interest in sulfur monoxide (SO) among astrochemists, spectroscopists, inorganic chemists, and organic chemists, its interaction with water remains largely unexplored. We report the first high level theoretical geometries for the two minimum energy complexes formed by sulfur monoxide and water, and we report energies using basis sets as large as aug-cc-pV(Q+d)Z and correlation effects through perturbative quadruple excitations. One structure of SO⋯H 2 O is hydrogen bonded and the other chalcogen bonded. The hydrogen bonded complex has an electronic energy of −2.71 kcal mol −1 and a zero kelvin enthalpy of −1.67 kcal mol −1 , while the chalcogen bonded complex has an electronic energy of −2.64 kcal mol −1 and a zero kelvin enthalpy of −2.00 kcal mol −1 . We also report the transition state between the two structures, which lies below the SO⋯H 2 O dissociation limit, with an electronic energy of −1.26 kcal mol −1 and an enthalpy of −0.81 kcal mol −1 . These features are much sharper than for the isovalent complex of O 2 and H 2 O, which only possesses one weakly bound minimum, so we further analyze the structures with open-shell SAPT0. We find that the interactions between O 2 and H 2 O are uniformly weak, but the SO⋯H 2 O complex surface is governed by the superior polarity and polarizability of SO, as well as the diffuse electron density provided by sulfur's extra valence shell. 
    more » « less
  3. To cut CO2emissions, we propose to directly convert shale gas into value-added products with a new H2/O2co-transport membrane (HOTM) reactor. A Multiphysics model has been built to simulate the membrane and the catalytic bed with parameters obtained from experimental validation. The model was used to compare C2 yield and CH4conversion rate between the membrane reactor and the state-of-the-art fixed-bed reactor with the same dimensions and operating conditions. The results indicate that (1) the membrane reactor is more efficient in consuming CH4for a given amount of fed O2. (2) The C2 selectivity of the membrane reactor is higher due to the gradual addition of O2into the reactor. (3) The current proposed membrane reactor can have a decent proton molar flux density but most of the proton molar flux will contribute to producing H2O on the feed side under the current operating conditions. The paper for the first-time projects the performance of the membrane reactor for combined H2O/H2removal and C2 production. It could be used as important guidance for experimentalists to design next generation natural gas conversion reactors.

     
    more » « less
  4. The optimized geometries, vibrational frequencies, and dissociation energies from MP2 and CCSD(T) computations with large correlation consistent basis sets are reported for (H2S)2and H2O/H2S. Anharmonic vibrational frequencies have also been computed with second‐order vibrational perturbation theory (VPT2). As such, the fundamental frequencies, overtones, and combination bands reported in this study should also provide a useful road map for future spectroscopic studies of the simple but important heterogeneous H2O/H2S dimer in which the hydrogen bond donor and acceptor can interchange, leading to two unique minima with very similar energies. Near the CCSD(T) complete basis set limit, the HOH⋯SH2configuration (H2O donor) lies only 0.2 kcal mol−1below the HSH⋯OH2structure (H2S donor). When the zero‐point vibrational energy is included, however, the latter configuration becomes slightly lower in energy than the former by <0.1 kcal mol−1. © 2018 Wiley Periodicals, Inc.

     
    more » « less