title: Matrix-Isolated Infrared Absorption Spectrum of CH2IOO Radical.
abstract: The peroxyiodomethyl radical, CH2IOO, was generated in cryogenic matrices using tandem supersonic nozzles. One hyperthermal nozzle decomposes diiodomethane (CH2I2) to generate intense beams of CH2I radicals, while the second nozzle continuously deposits O2/argon (Ar) on the matrix at 10 K. The CH2I and O2 in the Ar matrix react to produce the target peroxy radical (CH2IOO). The absorption spectra of the products are monitored with a Fourier transform infrared spectrometer. Eight of the 12 fundamental infrared bands for CH2IOO were observed in an argon matrix at 5 K. The experimental frequencies (cm(-1)) are ν3 = 1407.3, ν4 = 1230.4, ν5 = 1223.2, ν6 = 1085.3, ν7 = 919.9, ν8 = 839.9, ν9 = 567.5, and ν10 = 496.2. Additional confirmation for the vibrational assignment comes from a study of the CH2I(18)O(18)O isotopic species. The six observed frequencies (cm(-1)) for CH2I(18)O(18)O are ν3 = 1407.8, ν4 = 1228.0, ν6 = 1030.8, ν7 = 899.6, ν8 = 836.0, and ν10 = 494.6. Unlike CH2I(16)O(16)O, the ν5 and ν9 bands were not observed for CH2I(18)O(18)O. To guide the experimental analysis, ab initio calculations of the infrared spectrum based on second-order vibrational perturbation theory were performed using force fields computed with relativistic coupled-cluster methods. The experimental frequencies are shown to be in good agreement with the computed fundamental frequencies except for ν9 (for CH2IOO) and ν10 (for CH2I(18)O(18)O). Our findings were compared with the study by Lee and Lee conducted in a para-H2 matrix. The fundamental frequencies are in good agreement (within 6 cm(-1)) except for the two low-frequency modes, ν9 (for CH2IOO) and ν10 (for CH2I(18)O(18)O) likely due to different matrix shifts for para-H2 and Ar matrices. In addition, our calculations are in somewhat better agreement with the experiment values than the calculations by Lee and Lee. Our study also shows that reaction CH2I + O2 produces the peroxy radical CH2IOO in cold matrices (10 K) instead of Criegee intermediate CH2OO, which is generated in gas phase (300 K and low pressure); the same finding was also reported by Lee and Lee.
authors.affiliation: Jet Propulsion Laboratory, California Institute of Technology , 4800 Oak Grove Drive, Pasadena, California 91109-8099, United States.|Institute for Theoretical Chemistry, Department of Chemistry, University of Texas , Austin, Texas 78712, United States.
authors.forename: Xu
authors.initials: X
authors.lastname: Zhang
authors.affiliation: Jet Propulsion Laboratory, California Institute of Technology , 4800 Oak Grove Drive, Pasadena, California 91109-8099, United States.|Institute for Theoretical Chemistry, Department of Chemistry, University of Texas , Austin, Texas 78712, United States.
authors.forename: Stanley P
authors.initials: SP
authors.lastname: Sander
authors.affiliation: Jet Propulsion Laboratory, California Institute of Technology , 4800 Oak Grove Drive, Pasadena, California 91109-8099, United States.|Institute for Theoretical Chemistry, Department of Chemistry, University of Texas , Austin, Texas 78712, United States.
authors.forename: Lan
authors.initials: L
authors.lastname: Cheng
authors.affiliation: Jet Propulsion Laboratory, California Institute of Technology , 4800 Oak Grove Drive, Pasadena, California 91109-8099, United States.|Institute for Theoretical Chemistry, Department of Chemistry, University of Texas , Austin, Texas 78712, United States.
authors.forename: Venkatesan S
authors.initials: VS
authors.lastname: Thimmakondu
authors.affiliation: Jet Propulsion Laboratory, California Institute of Technology , 4800 Oak Grove Drive, Pasadena, California 91109-8099, United States.|Institute for Theoretical Chemistry, Department of Chemistry, University of Texas , Austin, Texas 78712, United States.
authors.forename: John F
authors.initials: JF
authors.lastname: Stanton