title: The gas-phase structure of the asymmetric, trans-dinitrogen tetroxide (N2O4), formed by dimerization of nitrogen dioxide (NO2), from rotational spectroscopy and ab initio quantum chemistry.
abstract: We report the first experimental gas-phase observation of an asymmetric, trans-N2O4formed by the dimerization of NO2. In additional to the dominant14N216O4species, rotational transitions have been observed for all species with single15N and18O substitutions as well as several multiply substituted isotopologues. These transitions were used to determine a complete substitution structure as well as an r0structure from the fitted zero-point averaged rotational constants. The determined structure is found to be that of an ON-O-NO2linkage with the shared oxygen atom closer to the NO2than the NO (1.42 vs 1.61 Å). The structure is found to be nearly planar with a trans O-N-O-N linkage. From the spectra of the14N15NO4species, we were able to determine the nuclear quadrupole coupling constants for each specific nitrogen atom. The equilibrium structure determined by ab initio quantum chemistry calculations is in excellent agreement with the experimentally determined structure. No spectral evidence of the predicted asymmetric, cis-N2O4was found in the spectra.
authors.affiliation: Department of Chemistry, University of Virginia, Charlottesville, Virginia 22932, USA.
authors.forename: Nathan A
authors.initials: NA
authors.lastname: Seifert
authors.affiliation: Department of Chemistry, University of Virginia, Charlottesville, Virginia 22932, USA.
authors.forename: Daniel P
authors.identifier: 0000000301539158
authors.initials: DP
authors.lastname: Zaleski
authors.affiliation: Department of Chemistry, University of Virginia, Charlottesville, Virginia 22932, USADepartments of Chemistry and Physics, University of Virginia, Charlottesville, Virginia 22932, USADepartment of Chemistry, Amherst College, Amherst, Massachusetts 01002, USADepartment of Chemistry and Quantum Theory Project, University of Florida, Gainesville, Florida 32603, USA.
authors.forename: Robert
authors.initials: R
authors.lastname: Fehnel
authors.affiliation: Department of Chemistry, University of Virginia, Charlottesville, Virginia 22932, USA.
authors.forename: Mausumi
authors.identifier: 0000000230578239
authors.initials: M
authors.lastname: Goswami
authors.affiliation: Department of Chemistry, University of Virginia, Charlottesville, Virginia 22932, USA.
authors.forename: Brooks H
authors.initials: BH
authors.lastname: Pate
authors.affiliation: Departments of Chemistry and Physics, University of Virginia, Charlottesville, Virginia 22932, USA.
authors.forename: Kevin K
authors.identifier: 0000000335288641
authors.initials: KK
authors.lastname: Lehmann
authors.affiliation: Department of Chemistry, Amherst College, Amherst, Massachusetts 01002, USA.
authors.forename: Helen O
authors.initials: HO
authors.lastname: Leung
authors.affiliation: Department of Chemistry, Amherst College, Amherst, Massachusetts 01002, USA.
authors.forename: Mark D
authors.identifier: 0000000240524840
authors.initials: MD
authors.lastname: Marshall
authors.affiliation: Department of Chemistry and Quantum Theory Project, University of Florida, Gainesville, Florida 32603, USA.
authors.forename: John F
authors.initials: JF
authors.lastname: Stanton