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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
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We report results from experiments with the quinoline-O2 complex, which was photodissociated using light near 312 nm. Photodissociation resulted in formation of the lowest excited state of oxygen, O2 a 1Δg, which we detected using resonance enhanced multiphoton ionization and velocity map ion imaging. The O2+ ion image allowed for a determination of the center-of-mass translational energy distribution, P(ET), following complex dissociation. We also report results of electronic structure calculations for the quinoline singlet ground state and lowest energy triplet state. From the CCSD/aug-cc-pVDZ//(U)MP2/cc-pVDZ calculations, we determined the lowest energy triplet state to have ππ* electronic character and to be 2.69 eV above the ground state. We also used electronic structure calculations to determine the geometry and binding energy for several quinoline-O2 complexes. The calculations indicated that the most strongly bound complex has a well depth of about 0.11 eV and places the O2 moiety above and approximately parallel to the quinoline ring system. By comparing the experimental P(ET) with the energy for the singlet ground state and the lowest energy triplet state, we concluded that the quinoline product was formed in the lowest energy triplet state. Finally, we found the experimental P(ET) to be in agreement with a Prior translational energy distribution, which suggests a statistical dissociation for the complex.more » « less
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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/z 332 andm/z 318. 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.
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- https://doi.org/10.1021/jacs.2c08315
