Title

Computational investigations on S-nitrosothiols.

Date of Award

2005

Degree Type

Thesis

Degree Name

M.Sc.

Department

Chemistry and Biochemistry

Keywords

Chemistry, Biochemistry.

Rights

CC BY-NC-ND 4.0

Abstract

Several computational investigations on the properties of S-nitrosothiols (RSNOs) and other interactions with the biochemically important Cu + ions are described. In Chapter 3, the ability of conventional electron correlation (MP2 and QCISD) and DFT (B3LYP and B3P86) methods to provide accurate and reliable structures and homolytic S--N BDEs, for a range of RSNOs is considered. With a suitable large basis set, i.e., 6-311+G(2df,p) or larger, the different methods generally give optimized structures in close agreement with each other; the B3LYP method consistently overestimates r(S--N). The trends observed are due in part to the fact that the RS--NO bond does not possess considerable double-bond character as previously suggested, but rather is a long single S--N bond. For BDEs, B3P86/6-311+G(2df,p) consistently gives best agreement with higher accuracy methods. For all RSNOs, QCISD significantly underestimates BDEs, Of the methods considered, B3P86/6-311+G(2df,p) is found to perform the best for obtaining optimized structures and homolytic S--N BDEs of S-nitrosothiols. (Abstract shortened by UMI.)Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis2004 .B32. Source: Masters Abstracts International, Volume: 44-01, page: 0350. Thesis (M.Sc.)--University of Windsor (Canada), 2005.