skip to main content


Title: Branching Ratio for O + H 3 + Forming OH + + H 2 and H 2 O + + H
Abstract The gas-phase reaction of O + H 3 + has two exothermic product channels: OH + + H 2 and H 2 O + + H. In the present study, we analyze experimental data from a merged-beams measurement to derive thermal rate coefficients resolved by product channel for the temperature range from 10 to 1000 K. Published astrochemical models either ignore the second product channel or apply a temperature-independent branching ratio of 70% versus 30% for the formation of OH + + H 2 versus H 2 O + + H, respectively, which originates from a single experimental data point measured at 295 K. Our results are consistent with this data point, but show a branching ratio that varies with temperature reaching 58% versus 42% at 10 K. We provide recommended rate coefficients for the two product channels for two cases, one where the initial fine-structure population of the O( 3 P J ) reactant is in its J = 2 ground state and the other one where it is in thermal equilibrium.  more » « less
Award ID(s):
2002461
NSF-PAR ID:
10331891
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
The Astrophysical Journal
Volume:
927
Issue:
1
ISSN:
0004-637X
Page Range / eLocation ID:
47
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    The water reactivity of the boroauride complex ([Au(B 2 P 2 )][K(18-c-6)]; (B 2 P 2 , 9,10-bis(2-(diisopropylphosphino)-phenyl)-9,10-dihydroboranthrene) and its corresponding two-electron oxidized complex, Au(B 2 P 2 )Cl, are presented. Au(B 2 P 2 )Cl is tolerant to H 2 O and forms the hydroxide complex Au(B 2 P 2 )OH in the presence of H 2 O and triethylamine. [Au(B 2 P 2 )]Cl and [Au(B 2 P 2 )]OH are poor Lewis acids as judged by the Gutmann–Becket method, with [Au(B 2 P 2 )]OH displaying facile hydroxide exchange between B atoms of the DBA ring as evidenced by variable temperature NMR spectroscopy. The reduced boroauride complex [Au(B 2 P 2 )] − reacts with 1 equivalent of H 2 O to produce a hydride/hydroxide product, [Au(B 2 P 2 )(H)(OH)] − , that rapidly evolves H 2 upon further H 2 O reaction to yield the dihydroxide compound, [Au(B 2 P 2 )(OH) 2 ] − . [Au(B 2 P 2 )]Cl can be regenerated from [Au(B 2 P 2 )(OH) 2 ] − via HCl·Et 2 O, providing a synthetic cycle for H 2 evolution from H 2 O enabled by O–H oxidative addition at a diboraanthracene unit. 
    more » « less
  2. Abstract

    We recently reported a detailed investigation of the collision‐induced dissociation (CID) of [UO2(NO3)3]and [UO2(NO3)2(O2)]in a linear ion trap mass spectrometer (J. Mass Spectrom. DOI:10.1002/jms.4705). Here, we describe the CID of [UO2(NO3)(O2)]which is created directly by ESI, or indirectly by simple elimination of O2from [UO2(NO3)(O2)2]. CID of [UO2(NO3)(O2)]creates product ions as atm/z332 andm/z318. The former may be formed directly by elimination of O2, while the latter required decomposition of a nitrate ligand and elimination of NO2. DFT calculations identify a pathway by which both product ions can be generated, which involves initial isomerization of [UO2(NO3)(O2)]to create [UO2(O)(NO2)(O2)], from which elimination of NO2or O2will leave [UO2(O)(O2)]or [UO2(O)(NO2)], respectively. For the latter product ion, the composition assignment of [UO2(O)(NO2)]rather than [UO2(NO3)]is supported by ion‐molecule reaction behavior, and in particular, the fact that spontaneous addition of O2, which is predicted to be the dominant reaction pathway for [UO2(NO3)]is not observed. Instead, the species reacts with H2O, which is predicted to be the favored pathway for [UO2(O)(NO2)]. This result in particular demonstrates the utility of ion‐molecule reactions to assist the determination of ion composition. As in our earlier study, we find that ions such as [UO2(O)(NO2)]and [UO2(O)(O2)]form H2O adducts, and calculations suggest these species spontaneously rearrange to create dihydroxides.

     
    more » « less
  3. Abstract

    Organofunctionalized tetranuclear clusters [(MIICl)2(VIVO)2{((HOCH2CH2)(H)N(CH2CH2O))(HN(CH2CH2O)2)}2] (1, M=Co,2: M=Zn) containing an unprecedented oxometallacyclic {M2V2Cl2N4O8} (M=Co, Zn) framework have been prepared by solvothermal reactions. The new oxo‐alkoxide compounds were fully characterized by spectroscopic methods, magnetic susceptibility measurement, DFT and ab initio computational methods, and complete single‐crystal X‐ray diffraction structure analysis. The isostructural clusters are formed of edge‐sharing octahedral {VO5N} and trigonal bipyramidal {MO3NCl} units. Diethanolamine ligates the bimetallic lacunary double cubane core of1and2in an unusual two‐mode fashion, unobserved previously. In the crystalline state, the clusters of1and2are joined by hydrogen bonds to form a three‐dimensional network structure. Magnetic susceptibility data indicate weakly antiferromagnetic interactions between the vanadium centers [Jiso(VIV−VIV)=−5.4(1); −3.9(2) cm−1], and inequivalent antiferromagnetic interactions between the cobalt and vanadium centers [Jiso(VIV−CoII)=−12.6 and −7.5 cm−1] contained in1.

     
    more » « less
  4. Abstract

    A novel transition metal chalcohalide [Cr7S8(en)8Cl2]Cl3 ⋅ 2H2O, with [Cr7S8]5+dicubane cationic clusters, has been synthesized by a low temperature solvothermal method, using dimethyl sulfoxide (DMSO) and ethylenediamine (en) solvents. Ethylenediamine ligand exhibits bi‐ and monodentate coordination modes; in the latter case ethylenediamine coordinates to Cr atoms of adjacent clusters, giving rise to a 2D polymeric structure. Although magnetic susceptibility shows no magnetic ordering down to 1.8 K, a highly negative Weiss constant,θ=−224(2) K, obtained from Curie‐Weiss fit of inverse susceptibility, suggests strong antiferromagnetic (AFM) interactions betweenS=3/2 Cr(III) centers. Due to the complexity of the system with (2S+1)7=16384 microstates from seven Cr3+centers, a simplified model with only two exchange constants was used for simulations. Density‐functional theory (DFT) calculations yielded the two exchange constants to beJ1=−21.4 cm−1andJ2=−30.2 cm−1, confirming competing AFM coupling between the shared Cr3+center and the peripheral Cr3+ions of the dicubane cluster. The best simulation of the experimental data was obtained withJ1=−20.0 cm−1andJ2=−21.0 cm−1, in agreement with the slightly stronger AFM exchange within the triangles of the peripheral Cr3+ions as compared to the AFM exchange between the central and peripheral Cr3+ions. This compound is proposed as a synthon towards magnetically frustrated systems assembled by linking dicubane transition metal‐chalcogenide clusters into polymeric networks.

     
    more » « less
  5. Abstract

    Electrospray ionization (ESI) can produce a wide range of gas‐phase uranyl (UO22+) complexes for tandem mass spectrometry studies of intrinsic structure and reactivity. We describe here the formation and collision‐induced dissociation (CID) of [UO2(NO3)3]and [UO2(NO3)2(O2)]. Multiple‐stage CID experiments reveal that the complexes dissociate in reactions that involve elimination of O2, NO2, or NO3, and subsequent reactions of interesting uranyl‐oxo product ions with (neutral) H2O and/or O2were investigated. Density functional theory (DFT) calculations reproduce experimental results and show that dissociation of nitrate ligands, with ejection of neutral NO2, is favored for both [UO2(NO3)3]and [UO2(NO3)2(O2)]. DFT calculations also suggest that H2O adducts to products such as [UO2(O)(NO3)]spontaneously rearrange to create dihydroxides and that addition of O2is favored over addition of H2O to formally U(V) species.

     
    more » « less