An Accurate Quartic Force Field and Fundamental Frequencies for the Ozonide Anion: A Rare Positive Anharmonicity for the Antisymmetric Stretch

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Title:An Accurate Quartic Force Field and Fundamental Frequencies for the Ozonide Anion: A Rare Positive Anharmonicity for the Antisymmetric Stretch
Creators:
Lee, Timothy J.
Dateo, Christopher E.
Rubio, Mercedes
Roos, Björn O.
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 68, 1, pp. 189-201
Uncontrolled Keywords:<i>Ab initio</i> calculations, CCSD, Vibrational spectroscopy, Isotope effects, Ozone, Ozonide

Abstract

The CCSD(T) method has been used to compute a highly accurate quartic force field and fundamental frequencies for all <sup>16</sup>O and <sup>18</sup>O isotopomers of the ozonide anion. The CCSD and CASPT2 methods have also been used to verify the reliability of the CCSD(T) fundamental frequencies. The computed fundamental frequencies are in agreement with gas-phase experiments, but disagree with matrix isolation experiments for the antisymmetric stretch, ν<sub>3</sub>. CASPT2 calculations show that the antisymmetric part of the O<sub>3</sub><sup>-</sup> potential surface is sensitive to the external environment. It is concluded that the antisymmetric stretch exhibits a significant matrix shift in the matrix isolation experiments and that the matrix environment is not representative of the gas-phase environment for ozonide anion. It is hoped that the theoretical data provided here will aid in the interpretation of future high-resolution gas-phase experiments. <p>

Title:An Accurate Quartic Force Field and Fundamental Frequencies for the Ozonide Anion: A Rare Positive Anharmonicity for the Antisymmetric Stretch
Creators:
Lee, Timothy J.
Dateo, Christopher E.
Rubio, Mercedes
Roos, Björn O.
Uncontrolled Keywords:<i>Ab initio</i> calculations, CCSD, Vibrational spectroscopy, Isotope effects, Ozone, Ozonide
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:68
Number:1
Page Range:pp. 189-201
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20030189UNSPECIFIED
ID Code:2052
Item Type:Article
Deposited On:06 Feb 2009 17:15
Last Modified:06 Feb 2009 16:15

Citation

Lee, Timothy J.; Dateo, Christopher E.; Rubio, Mercedes; Roos, Björn O. (2003) An Accurate Quartic Force Field and Fundamental Frequencies for the Ozonide Anion: A Rare Positive Anharmonicity for the Antisymmetric Stretch. Collection of Czechoslovak Chemical Communications, 68 (1). pp. 189-201. ISSN 0010-0765

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