Trends in alkali metal hydrosulfides: A combined Fourier transform microwave/millimeter-wave spectroscopic study of KSH (X1A′)

M. P. Bucchino, P. M. Sheridan, J. P. Young, M. K L Binns, D. W. Ewing, Lucy M Ziurys

Research output: Contribution to journalArticle

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Abstract

The pure rotational spectrum of KSH (X1A′) has been measured using millimeter-wave direct absorption and Fourier transform microwave (FTMW) techniques. This work is the first gas-phase experimental study of this molecule and includes spectroscopy of KSD as well. In the millimeter-wave system, KSH was synthesized in a DC discharge from a mixture of potassium vapor, H2S, and argon; a discharge-assisted laser ablation source, coupled with a supersonic jet expansion, was used to create the species in the FTMW instrument. Five and three rotational transitions in the range 3-57 GHz were recorded with the FTMW experiment for KSH and KSD, respectively, in the K a = 0 component; in these data, potassium quadrupole hyperfine structure was observed. Five to six transitions with Ka = 0-5 were measured in the mm-wave region (260-300 GHz) for the two species. The presence of multiple asymmetry components in the mm-wave spectra indicates that KSH has a bent geometry, in analogy to other alkali hydrosulfides. The data were analyzed with an S-reduced asymmetric top Hamiltonian, and rotational, centrifugal distortion, and potassium electric quadrupole coupling constants were determined for both isotopolgues. The r0 geometry for KSH was calculated to be rS-H = 1.357(1) Å, rK-S = 2.806(1) Å, and θM-S-H (°) = 95.0 (1). FTMW measurements were also carried out on LiSH and NaSH; metal electric quadrupole coupling constants were determined for comparison with KSH. In addition, ab initio computations of the structures and vibrational frequencies at the CCSD(T)/6-311++G(3df,2pd) and CCSD(T)/aug-cc-pVTZ levels of theory were performed for LiSH, NaSH, and KSH. Overall, experimental and computational data suggest that the metal-ligand bonding in KSH is a combination of electrostatic and covalent forces.

Original languageEnglish (US)
Article number214307
JournalThe Journal of Chemical Physics
Volume139
Issue number21
DOIs
StatePublished - Dec 7 2013

Fingerprint

Alkali Metals
Millimeter waves
alkali metals
millimeter waves
Fourier transforms
Microwaves
trends
microwaves
potassium
Potassium
quadrupoles
Discharge (fluid mechanics)
Metals
Microwave measurement
Hamiltonians
Geometry
Argon
rotational spectra
Alkalies
Vibrational spectra

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Trends in alkali metal hydrosulfides : A combined Fourier transform microwave/millimeter-wave spectroscopic study of KSH (X1A′). / Bucchino, M. P.; Sheridan, P. M.; Young, J. P.; Binns, M. K L; Ewing, D. W.; Ziurys, Lucy M.

In: The Journal of Chemical Physics, Vol. 139, No. 21, 214307, 07.12.2013.

Research output: Contribution to journalArticle

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abstract = "The pure rotational spectrum of KSH (X1A′) has been measured using millimeter-wave direct absorption and Fourier transform microwave (FTMW) techniques. This work is the first gas-phase experimental study of this molecule and includes spectroscopy of KSD as well. In the millimeter-wave system, KSH was synthesized in a DC discharge from a mixture of potassium vapor, H2S, and argon; a discharge-assisted laser ablation source, coupled with a supersonic jet expansion, was used to create the species in the FTMW instrument. Five and three rotational transitions in the range 3-57 GHz were recorded with the FTMW experiment for KSH and KSD, respectively, in the K a = 0 component; in these data, potassium quadrupole hyperfine structure was observed. Five to six transitions with Ka = 0-5 were measured in the mm-wave region (260-300 GHz) for the two species. The presence of multiple asymmetry components in the mm-wave spectra indicates that KSH has a bent geometry, in analogy to other alkali hydrosulfides. The data were analyzed with an S-reduced asymmetric top Hamiltonian, and rotational, centrifugal distortion, and potassium electric quadrupole coupling constants were determined for both isotopolgues. The r0 geometry for KSH was calculated to be rS-H = 1.357(1) {\AA}, rK-S = 2.806(1) {\AA}, and θM-S-H (°) = 95.0 (1). FTMW measurements were also carried out on LiSH and NaSH; metal electric quadrupole coupling constants were determined for comparison with KSH. In addition, ab initio computations of the structures and vibrational frequencies at the CCSD(T)/6-311++G(3df,2pd) and CCSD(T)/aug-cc-pVTZ levels of theory were performed for LiSH, NaSH, and KSH. Overall, experimental and computational data suggest that the metal-ligand bonding in KSH is a combination of electrostatic and covalent forces.",
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