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Contribution to Book
Density Functional Calculation of the Structure and Electronic Properties of CunOn (n = 1−4) Clusters
Computational Science – ICCS 2009: 9th International Conference Baton Rouge, LA, USA, May 25-27, 2009 Proceedings, Part II (2009)
  • Gyun-Tack Bae, Department of Chemistry, Louisiana State University, Baton Rouge
  • Randall W. Hall, Department of Chemistry, Louisiana State University, Baton Rouge
Abstract
The formation, stability, and reactivity of chlorinated phenoxyl radicials was studied using ab initio methods. All 19 congeners from mono- to penta-chlorinated species were considered. The radical species are formed in combustion reactions via unimolecular scission of the phenoxyl-hydrogen bond or hydrogen atom abstraction by hydrogen atom or hydroxyl radical. The resulting radicals are stable with respect to unimolecular decomposition and reaction with molecular oxygen is relatively slow. Activation energies are similar to those of the phenoxyl radical for both the decomposition pathway and the reaction with molecular oxygen at the more reactive para-position. Calculations were performed with the model chemistries B3LYP/6-31G(d,p), BHandHLYP/6-31G(d,p), BHandHLYP/aug-cc-pVDZ and QCISD(T)/6-31G(d,p)//BHandHLYP/6-31G(d,p) (for selected reactions.) The results suggest the radicals are sufficiently stable and unreactive to be moderately persistent in the atmosphere, especially when associated with some types of particulate matter. An additivity analysis is made to decompose the relative energetics of the congeners into contributions from hydrogen bonding, resonance stabilization, and repulsive interactions. The results of this analysis correlate well with the results of the calculations.
Keywords
  • Free radical,
  • Ab initio,
  • Combustion
Disciplines
Publication Date
2009
Editor
Gabrielle Allen, Jarosław Nabrzyski, Edward Seidel, Geert Dick van Albada, Jack Dongarra, Peter M. A. Sloot
Publisher
Springer Berlin Heidelberg
Series
Lecture notes in computer science
ISBN
978-3-642-01972-2
DOI
10.1007/978-3-642-01973-9_14
Citation Information
Gyun-Tack Bae and Randall W. Hall. "Density Functional Calculation of the Structure and Electronic Properties of CunOn (n = 1−4) Clusters" Berlin, GermanyComputational Science – ICCS 2009: 9th International Conference Baton Rouge, LA, USA, May 25-27, 2009 Proceedings, Part II Vol. 5545 (2009) p. 122 - 130
Available at: http://works.bepress.com/randall_hall/3/