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The Structure and Cl-O Dissociation Energy of the ClOO Radical: Finally, the Right Answers for the Right Reason.

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Title: The Structure and Cl-O Dissociation Energy of the ClOO Radical: Finally, the Right Answers for the Right Reason.
Authors: Abbott, Adam S.1, Schaefer III, Henry F.1 ccq@uga.edu
Source: Journal of Physical Chemistry A. 3/8/2018, Vol. 122 Issue 9, p2604-2610. 7p.
Subjects: Radicals, Chlorine, Peroxy radicals, Ab initio quantum chemistry methods, Geometry, Electrons
Abstract: The chlorine peroxy radical (ClOO) has historically been a highly problematic system for theoretical studies. In particular, the erratic ab initio predictions of the Cl-O bond length reported in the literature thus far exhibit unacceptable errors with respect to the experimental structure. In light of the widespread disagreement observed, we present a careful and systematic investigation of the ClOO geometry toward the basis set and correlation limits of single reference ab initio theory, employing the cc-pVXZ (X = D, T, Q, 5, 6) basis sets extrapolated to the complete basis set limit and coupled cluster theory through single, double, triple, and perturbative quadruple excitations [CCSDT(Q)]. We demonstrate a considerable sensitivity of the Cl-O bond length to both electron correlation and basis set size. The CCSDT(Q)/CBS structure is found to be re(ClO) = 2.082, re(OO) = 1.208, and θe(ClOO) = 115.4°, in remarkable agreement with Endo's semi-experimentally determined values re(ClO) = 2.084(1), re(OO) = 1.206(2), and θe(ClOO) = 115.4(1)°. Moreover, we compute a Cl-O bond dissociation energy of 4.77 kcal mol-1, which is likewise in excellent agreement with the most recent experimental value of 4.69 ± 0.10 kcal mol-1. [ABSTRACT FROM AUTHOR]
Copyright of Journal of Physical Chemistry A is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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DbLabel: Engineering Source
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  Data: The Structure and Cl-O Dissociation Energy of the ClOO Radical: Finally, the Right Answers for the Right Reason.
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  Data: <searchLink fieldCode="AR" term="%22Abbott%2C+Adam+S%2E%22">Abbott, Adam S.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Schaefer+III%2C+Henry+F%2E%22">Schaefer III, Henry F.</searchLink><relatesTo>1</relatesTo><i> ccq@uga.edu</i>
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Chemistry+A%22">Journal of Physical Chemistry A</searchLink>. 3/8/2018, Vol. 122 Issue 9, p2604-2610. 7p.
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  Data: <searchLink fieldCode="DE" term="%22Radicals%22">Radicals</searchLink><br /><searchLink fieldCode="DE" term="%22Chlorine%22">Chlorine</searchLink><br /><searchLink fieldCode="DE" term="%22Peroxy+radicals%22">Peroxy radicals</searchLink><br /><searchLink fieldCode="DE" term="%22Ab+initio+quantum+chemistry+methods%22">Ab initio quantum chemistry methods</searchLink><br /><searchLink fieldCode="DE" term="%22Geometry%22">Geometry</searchLink><br /><searchLink fieldCode="DE" term="%22Electrons%22">Electrons</searchLink>
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  Data: The chlorine peroxy radical (ClOO) has historically been a highly problematic system for theoretical studies. In particular, the erratic ab initio predictions of the Cl-O bond length reported in the literature thus far exhibit unacceptable errors with respect to the experimental structure. In light of the widespread disagreement observed, we present a careful and systematic investigation of the ClOO geometry toward the basis set and correlation limits of single reference ab initio theory, employing the cc-pVXZ (X = D, T, Q, 5, 6) basis sets extrapolated to the complete basis set limit and coupled cluster theory through single, double, triple, and perturbative quadruple excitations [CCSDT(Q)]. We demonstrate a considerable sensitivity of the Cl-O bond length to both electron correlation and basis set size. The CCSDT(Q)/CBS structure is found to be re(ClO) = 2.082, re(OO) = 1.208, and θe(ClOO) = 115.4°, in remarkable agreement with Endo's semi-experimentally determined values re(ClO) = 2.084(1), re(OO) = 1.206(2), and θe(ClOO) = 115.4(1)°. Moreover, we compute a Cl-O bond dissociation energy of 4.77 kcal mol-1, which is likewise in excellent agreement with the most recent experimental value of 4.69 ± 0.10 kcal mol-1. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Journal of Physical Chemistry A is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1021/acs.jpca.8b00394
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      – Code: eng
        Text: English
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        Type: general
      – SubjectFull: Chlorine
        Type: general
      – SubjectFull: Peroxy radicals
        Type: general
      – SubjectFull: Ab initio quantum chemistry methods
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      – SubjectFull: Geometry
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      – SubjectFull: Electrons
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      – TitleFull: The Structure and Cl-O Dissociation Energy of the ClOO Radical: Finally, the Right Answers for the Right Reason.
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            – D: 08
              M: 03
              Text: 3/8/2018
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            – TitleFull: Journal of Physical Chemistry A
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