The New Jersey Institute of Technology's
Electronic Theses & Dissertations Project

Title:	Quantitative evaluation of substituent effects on stabilization energies of strained and unsaturated molecules
Author:	Stevenson, Tyler Arthur
View Online:	njit-etd1984-033 (v, 123 pages ~ 3.4 MB pdf)
Department:	Department of Chemical Engineering and Chemistry
Degree:	Master of Science
Program:	Chemistry
Document Type:	Thesis
Advisory Committee:	Greenberg, Arthur (Committee chair) Liebman, Joel F. (Committee member) Venanzi, Carol A. (Committee member)
Date:	1984-05
Keywords:	Molecular dynamics Thermodynamics
Availability:	Unrestricted
Abstract:	Thermodynamic stabilization energies are presented for a series of monosubstituted vinyl, cyclopropyl, ethynyl, and phenyl compounds. The energies are calculated using ab initio molecular orbital calculations at the 4-31G level, and also with published experimental heat of formation data. Correlation analyses are then attempted with the dual substituent parameter approach with the stabilization energies. The analyses are also attempted with a triple-parameter approach using Topsom's theoretically calculated X, F, and Ro constants. Among the findings are the facts that π-donating substituents correlate well, while π-accepting substituents do not. Indications of the relative sensitivities of hydrocarbon frameworks to substituent electrostatic and resonance effects are analyzed. Photoelectron spectroscopy and carbon-13 chemical shift data of the substituted olefinic compounds are also examined to provide further insights.