Complexes Pairing Aliphatic Amines with Hydroxyl and Hydroperoxyl Radicals: A Computational Study

Authors

M. Solimannejad
C. J. Neilsen
Steve Scheiner, utah state universityFollow

Document Type

Article

Journal/Book Title

Chemical Physics Letters

Publication Date

12-2008

Publisher

Elsevier

Volume

466

Issue

4-6

First Page

136

Last Page

140

Abstract

Quantum calculations are used to analyze the nature and strength of binding of complexes pairing aliphatic amines with the HO and HOO radicals, with particular emphasis on the comparison of HO with HOO. Complexes are stabilized by N⋯HO(O) H-bonds involving the N lone pair. The OOH radical binds more strongly in all cases than does OH, and shows a longer stretch of its OH bond, as well as a greater red shift of this bond’s stretching frequency. MP2/6-311++G(3df, 3pd) binding energies vary from 28 kJ/mol for CH₃NH₂⋯HO to a maximum of 56 kJ/mol for (CH₃)₂NH⋯HOO. The reliability of a new hybrid meta exchange-correlation functional, M05-2X, compares favorably with MP2, generally better than B3LYP.

Recommended Citation

Solimannejad, M.; Neilsen, C. J.; and Scheiner, Steve, "Complexes Pairing Aliphatic Amines with Hydroxyl and Hydroperoxyl Radicals: A Computational Study" (2008). Chemistry and Biochemistry Faculty Publications. Paper 561.
https://digitalcommons.usu.edu/chem_facpub/561