Part One: The Quantitative Prediction and Analysis of Enthalpies for The Interaction of Gas Phase Ion-Ion, Gas Phase Ion-Molecule, and Molecule-Molecule Lewis Acid-Base Systems. Part Two: The Study of Intervalence Transfer in Mixed Valence Systems Using Time Domain Reflectometry

In Part One, the equation -(DELTA)H = e(,A)e(,B) + c(,A)c(,B) + t(,A)t(,B) where the subscripts A and B refer to acid and base correlates the enthalpy of Lewis acid-base adduct formation for molecule-molecule, gas phase ion-molecule, and gas phase ion-ion interactions. The parameters obtained are interpreted in terms of electrostatic, covalent, and electron transfer nature of interactions and trends in the parameters are found to agree with qualitative chemical intuition regarding acid-base properties and a semiempirical justification for the electron transfer term is presented. New insights regarding the comparison of gas phase and solution data are provided. The quantitative correlation can be used to indicate instances where variations may occur in the geometry of acid-base adducts. The existence of bonding contributions other than sigma-bond formation is also suggested by this correlation.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Kroeger, Michael Kevin

• Chemistry, Inorganic

Identifier

(UMI)AAI8203507

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70161