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Title: Isomers of NCO{sub 2}: IR-absorption spectra of ONCO in solid Ne

Abstract

Irradiation of a Ne matrix sample containing NO and CO near 4 K with an ArF excimer laser at 193 nm yielded new lines at 2045.1 and 968.0 cm{sup -1} that were depleted upon secondary photolysis at 308 nm. These lines are assigned to C=O stretching and mixed stretching modes of ONCO, based on results of {sup 15}N-, {sup 13}C-, and {sup 18}O-isotopic experiments and quantum-chemical calculations. These calculations using density-functional theory (B3LYP and PW91PW91/aug-cc-pVTZ) predict five stable isomers of NCO{sub 2}: ONCO, NCOO, N-cyc-CO{sub 2}, CNOO, and cyc-CNOO, listed in order of increasing energy. According to B3LYP calculations, ONCO has a trans configuration, with bond angles of AONC congruent with 136.3 deg. and ANOC congruent with 160.7 deg. Calculated vibrational wave numbers, IR intensities, {sup 15}N-, {sup 13}C-, and {sup 18}O-isotopic shifts for ONCO agree satisfactorily with experimental results. ONCO was formed from reaction of CO with NO in its excited state.

Authors:
;  [1];  [2];  [2]
  1. Department of Chemistry, National Tsing Hua University, 101, Sec. 2, Kuang Fu Road, Hsinchu 30013, Taiwan (China)
  2. (China)
Publication Date:
OSTI Identifier:
20723190
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 123; Journal Issue: 17; Other Information: DOI: 10.1063/1.2062267; (c) 2005 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTRA; BOND ANGLE; CARBON 13; CARBON MONOXIDE; DENSITY FUNCTIONAL METHOD; EXCIMER LASERS; INFRARED SPECTRA; IRRADIATION; ISOMERS; MATRIX ISOLATION; NITRIC OXIDE; NITROGEN 15; OXYGEN 18; PHOTOLYSIS; VIBRATIONAL STATES

Citation Formats

Wu, Y.-J., Lee, Y.-P., Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, 1001, Ta-Hsueh Road, Hsinchu 30013, Taiwan, and Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan. Isomers of NCO{sub 2}: IR-absorption spectra of ONCO in solid Ne. United States: N. p., 2005. Web. doi:10.1063/1.2062267.
Wu, Y.-J., Lee, Y.-P., Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, 1001, Ta-Hsueh Road, Hsinchu 30013, Taiwan, & Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan. Isomers of NCO{sub 2}: IR-absorption spectra of ONCO in solid Ne. United States. doi:10.1063/1.2062267.
Wu, Y.-J., Lee, Y.-P., Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, 1001, Ta-Hsueh Road, Hsinchu 30013, Taiwan, and Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan. Tue . "Isomers of NCO{sub 2}: IR-absorption spectra of ONCO in solid Ne". United States. doi:10.1063/1.2062267.
@article{osti_20723190,
title = {Isomers of NCO{sub 2}: IR-absorption spectra of ONCO in solid Ne},
author = {Wu, Y.-J. and Lee, Y.-P. and Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, 1001, Ta-Hsueh Road, Hsinchu 30013, Taiwan and Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan},
abstractNote = {Irradiation of a Ne matrix sample containing NO and CO near 4 K with an ArF excimer laser at 193 nm yielded new lines at 2045.1 and 968.0 cm{sup -1} that were depleted upon secondary photolysis at 308 nm. These lines are assigned to C=O stretching and mixed stretching modes of ONCO, based on results of {sup 15}N-, {sup 13}C-, and {sup 18}O-isotopic experiments and quantum-chemical calculations. These calculations using density-functional theory (B3LYP and PW91PW91/aug-cc-pVTZ) predict five stable isomers of NCO{sub 2}: ONCO, NCOO, N-cyc-CO{sub 2}, CNOO, and cyc-CNOO, listed in order of increasing energy. According to B3LYP calculations, ONCO has a trans configuration, with bond angles of AONC congruent with 136.3 deg. and ANOC congruent with 160.7 deg. Calculated vibrational wave numbers, IR intensities, {sup 15}N-, {sup 13}C-, and {sup 18}O-isotopic shifts for ONCO agree satisfactorily with experimental results. ONCO was formed from reaction of CO with NO in its excited state.},
doi = {10.1063/1.2062267},
journal = {Journal of Chemical Physics},
number = 17,
volume = 123,
place = {United States},
year = {Tue Nov 01 00:00:00 EST 2005},
month = {Tue Nov 01 00:00:00 EST 2005}
}
  • Irradiation of an Ar matrix sample containing O{sub 3} and CS{sub 2} with a KrF excimer laser at 248 nm yielded new lines at 1402.1 (1404.7), 1056.2 (1052.7), and 622.3 (620.5) cm-1; numbers in parentheses correspond to species in a minor matrix site. Secondary photolysis at 308 nm diminished these lines and produced mainly OCS and SO{sub 2}. Annealing of this matrix to 30 K yielded a second set of new lines at 1824.7 and 617.8 cm-1. The first set of lines are assigned to C=S stretching, O-S stretching, and S-C stretching modes of carbon disulfide S-oxide, OSCS; and themore » second set of lines are assigned to C=O stretching and OCS bending modes of dithiiranone, O(CS{sub 2}), respectively, based on results of {sup 34}S- and {sup 18}O-isotopic experiments and quantum-chemical calculations. These calculations using density-functional theory (B3LYP/aug-cc-pVTZ) predict four stable isomers of OCS{sub 2}: O(CS{sub 2}), SSCO, OSCS, and SOCS, listed in order of increasing energy. According to calculations, O(CS{sub 2}) has a cyclic CS{sub 2} moiety and is the most stable isomer of OCS{sub 2}. OSCS is planar, with bond angles anguprOSC congruent with 111.9 deg. and anguprSCS congruent with 177.3 deg.; it is less stable than SSCO and O(CS{sub 2}) by {approx}102 and 154 kJ mol-1, respectively, and more stable than SOCS by {approx}26 kJ mol-1. Calculated vibrational wave numbers, IR intensities, {sup 34}S- and {sup 18}O-isotopic shifts for OSCS and O(CS{sub 2}) fit satisfactorily with experimental results.« less
  • The optimized geometries and vibrational frequencies of neutral and anionic NCO and NCS isomers, CH/sub 2/NCH/sub 2/, and CH/sub 2/N are reported at the SCF level employing the 6-31G* basis set. NCO, CNO, and CON are found as minima for the neutral NCO isomers. For the anions, only NCO/sup -/) and CNO/sup -/ are stable structures. In case of the NCS isomers, only NCS and CNS are minima for neutral and anionic species. The adiabatic electron affinities and vertical detachment energies are determined at the MP2/6-31+G*//6-31G* + ZPE level. The results are in excellent agreement with recent experimentally derived datamore » reported for NCO, NCS, CH/sub 2/NCH/sub 2/, and CH/sub 2/N.« less
  • Molecular complexes of H/sub 2/O, H/sub 2/O/sub 2/, CO, and CO/sub 2/ in solid O/sub 2/ have been prepared by a conventional matrix deposition method using an appropriate gas mixture. FTIR spectra and vibrational assignments of matrix-isolated H/sub 2/O dimer and trimer, H/sub 2/O.CO/sub 2/, H/sub 2/O.CO, H/sub 2/O.H/sub 2/O/sub 2/, and H/sub 2/O/sub 2/.nCO in solid O/sub 2/ are presented. Hydrogen bonds of the type O...H-O involving H/sub x/O/sub z/ species and C...H-O involving H/sub x/O/sub z/.nCO species are found except for H/sub 2/O.CO/sub 2/. In the H/sub 2/O.H/sub 2/O/sub 2/ complex, H/sub 2/O/sub 2/ is an electron acceptormore » (acid) and H/sub 2/O is an electron donar (base). The frequency shift of the O-H stretch in the electron acceptor molecule of the complex increases in order of H/sub 2/O.CO, H/sup 2/O/sub 2/.CO, (H/sub 2/O)/sub 2/, and H/sub 2/O.H/sub 2/O/sub 2/. 41 references, 6 figures, 6 tables.« less
  • Near-ultraviolet absorption spectra for the I(1/2)/sub u/..-->..II(1/2)/sub g/ transition have been calculated for Ne/sup +//sub 2/, Ar/sup +//sub 2/, Kr/sup +//sub 2/, and Xe/sup +//sub 2/ using ab initio configuration interaction methods. The spectra are all similar except that the position of maximum absorption shifts to longer wavelength for the heavier rare gases. The absorption cross sections are tabulated at the wavelengths of the KrF, XeBr, XeCl, and XeF lasers.