Use of Ab Initio Theory in Studying Various Chemical Systems
AIR FORCE INST OF TECH WRIGHT-PATTERSON AFB OH
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Using ab initio calculations to supplement existing experimental data, a variety of chemical phenomena have been investigated. These include the effects of substituents on altering carbon-hydrogen and silicon-hydrogen bond strengths, the mode by which the empty orbital on boron alters the properties of an adjacent phosphorous atom, and the effect of substituents on the singlet- triplet energy gap in a non-Kekule molecule. It has been found that substituents can alter the strength of carbon-hydrogen and silicon-hydrogen bonds through both pi delocalization and omega electron donationwithdrawal. The prediction has been made that two BH2 groups cooperate and hence increase the calculated pi bond strength in diboryl phosphine. Last, that the strength of the carbonyl bond has been shown to be largely responsible for reducing the singlet-triplet energy gap in oxyallyl to near degeneracy and in causing dimethyloxyallyl to have a predicted singlet electronic ground state. Thesis.
- Physical Chemistry