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Author Amberger, Brent K. ♦ Esselman, Brian J. ♦ Woods, R. Claude ♦ McMahon, Robert J. ♦ Stanton, John F.
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ♦ ACCURACY ♦ CORRECTIONS ♦ EQUILIBRIUM ♦ GHZ RANGE ♦ HAMILTONIANS ♦ HYDRAZOIC ACID ♦ INTERACTIONS ♦ ROTATION ♦ SPECTRA ♦ SPECTROSCOPY
Abstract The millimeter-wave spectrum of hydrazoic acid (HN{sub 3}) was analyzed in the frequency region of 235-450 GHz. Transitions from a total of 14 isotopologues were observed and fit using the A-reduced or S-reduced Hamiltonian. Coupled-cluster calculations were performed to obtain a theoretical geometry, as well as rotation-vibration interaction corrections. These calculated vibration-rotation correction terms were applied to the experimental rotational constants to obtain mixed theoretical/experimental equilibrium rotational constants (A{sub e}, B{sub e}, and C{sub e}). These equilibrium rotational constants were then used to obtain an equilibrium (R{sub e}) structure using a least-squares fitting routine. The R{sub e} structural parameters are consistent with a previously published R{sub s} structure, largely falling within the uncertainty limits of that R{sub s} structure. The present R{sub e} geometric parameters of HN{sub 3} are determined with exceptionally high accuracy, as a consequence of the large number of isotopologues measured experimentally and the sophisticated (coupled-cluster theoretical treatment (CCSD(T))/ANO2) of the vibration-rotation interactions. The R{sub e} structure exhibits remarkable agreement with the CCSD(T)/cc-pCV5Z predicted structure, validating both the accuracy of the ab initio method and the claimed uncertainties of the theoretical/experimental structure determination.
ISSN 00219606
Educational Use Research
Learning Resource Type Article
Publisher Date 2015-09-14
Publisher Place United States
Journal Journal of Chemical Physics
Volume Number 143
Issue Number 10


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