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Broadband Fourier transform rotational spectroscopy for structure determination: The water heptamer
Chemical Physics Letters
  • Cristóbal Pérez, University of Virginia
  • Simon Lobsiger, University of Virginia
  • Nathan A Seifert, University of Virginia
  • Daniel P. Zaleski, University of Virginia
  • Berhane Temelso, Bucknell University
  • George C. Shields, Bucknell University
  • Zbigniew Kisiel, Polish Academy of Sciences
  • Brooks H. Pate, University of Virginia
Publication Date

Over the recent years chirped-pulse, Fourier-transform microwave (CP-FTMW) spectrometers have chan- ged the scope of rotational spectroscopy. The broad frequency and large dynamic range make possible structural determinations in molecular systems of increasingly larger size from measurements of heavy atom (13C, 15N, 18O) isotopes recorded in natural abundance in the same spectrum as that of the parent isotopic species. The design of a broadband spectrometer operating in the 2–8 GHz frequency range with further improvements in sensitivity is presented. The current CP-FTMW spectrometer performance is benchmarked in the analyses of the rotational spectrum of the water heptamer, (H2O)7, in both 2– 8 GHz and 6–18 GHz frequency ranges. Two isomers of the water heptamer have been observed in a pulsed supersonic molecular expansion. High level ab initio structural searches were performed to pro- vide plausible low-energy candidates which were directly compared with accurate structures provided from broadband rotational spectra. The full substitution structure of the most stable species has been obtained through the analysis of all possible singly-substituted isotopologues (H218O and HDO), and a least-squares rm(1) geometry of the oxygen framework determined from 16 different isotopic species compares with the calculated O–O equilibrium distances at the 0.01 Å level.

Citation Information
Cristóbal Pérez, Simon Lobsiger, Nathan A Seifert, Daniel P. Zaleski, et al.. "Broadband Fourier transform rotational spectroscopy for structure determination: The water heptamer" Chemical Physics Letters (2013) p. 1 - 15
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