Examining transition metal hydrosulfides: The pure rotational spectrum of ZnSH (X̃2A′)
AffiliationUniv Arizona, Dept Chem & Biochem
MetadataShow full item record
PublisherAMER INST PHYSICS
CitationExamining transition metal hydrosulfides: The pure rotational spectrum of ZnSH (X̃2A′) 2017, 147 (15):154313 The Journal of Chemical Physics
JournalThe Journal of Chemical Physics
RightsRights managed by AIP Publishing LLC.
Collection InformationThis item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at email@example.com.
AbstractThe pure rotational spectrum of the ZnSH ((X) over tilde (2)A') radical has been measured using millimeter-wave direct absorption and Fourier transform microwave (FTMW) methods across the frequency range 18-468 GHz. This work is the first gas-phase detection of ZnSH by any spectroscopic technique. Spectra of the (ZnSH)-Zn-66, (ZnSH)-Zn-68, and (ZnSD)-Zn-64 isotopologues were also recorded. In the mm-wave study, ZnSH was synthesized in a DC discharge by the reaction of zinc vapor, generated by a Broidatype oven, with H2S; for FTMW measurements, the radical was made in a supersonic jet expansion by the same reactants but utilizing a discharge-assisted laser ablation source. Between 7 and 9 rotational transitions were recorded for each isotopologue. Asymmetry components with K-a = 0 through 6 were typically measured in the mm-wave region, each split into spin-rotation doublets. In the FTMW spectra, hyperfine interactions were also resolved, arising from the hydrogen or deuterium nuclear spins of I = 1/2 or I = 1, respectively. The data were analyzed using an asymmetric top Hamiltonian, and rotational, spin-rotation, and magnetic hyperfine parameters were determined for ZnSH, as well as the quadrupole coupling constant for ZnSD. The observed spectra clearly indicate that ZnSH has a bent geometry. The r(m)((1)) structure was determined to be r(Zn-S) = 2.213(5) angstrom, r(S-H) = 1.351(3) angstrom, and theta(Zn-S-H) = 90.6(1)degrees, suggesting that the bonding occurs primarily through sulfur p orbitals, analogous to H2S. The hyperfine constants indicate that the unpaired electron in ZnSH primarily resides on the zinc nucleus. Published by AIP Publishing.
Note12 month embargo; Published online: 20 October 2017
VersionFinal published version