Structure and Rearrangements of Carbocations. The Isotopic Perturbation Method

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In this project ("Structure and Rearrangement of Carbocations. The Isotopic Perturbation Method") in the Organic Dynamics Program, Professor Martin Saunders of the Chemistry Department at Yale University will continue studies on the development and applications of the isotopic perturbation method. The focus of this project will be the investigation of the fundamental properties of reactive carbocations. This project will be focussed on the extension of the isotopic perturbation method to study the cooperative effects of multiple deuteration which produces equilibrium isotope effects that are nonlinear functions of the number of deuterium atoms. Experimental evidence will be obtained from investigations of the angular dependence of the isotope effects in rapid processes which include rotation around single bonds that varies dihedral angles between carbocation orbitals and carbon-hydrogen and carbon-carbon bonds. Ab initio quantum mechanical calculations will be performed to predict the energies and structures of carbocations and to predict equilibrium isotope effects which will be compared with the experimental results.