Rydberg series of calcium monofluoride : spectrum, structure, and dynamics

• Main Author: Kay, Jeffrey J
• Other Authors: Robert W. Field.
• Format: Others
• Language: English
• Published: Massachusetts Institute of Technology 2008
• Subjects: Chemistry.
• Online Access: http://hdl.handle.net/1721.1/40972

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2007. === Includes bibliographical references. === This thesis summarizes progress toward the ultimate goal of building a complete structural and dynamical model for the CaF molecule. The quantum defects of the Rydberg series of the molecule, as well as their dependences on the internuclear distance and the collision energy of the outer electron, are determined through a quantum defect theory fit of an extensive data set that contains almost all of the electronic states of the molecule that have been observed to date. The result is a global representation of all possible one-electron scattering processes in approximately 90 quantum defect parameters. The utility of such a representation is then demonstrated; the equilibrium quantum defects are used to explore the interaction between electronic and rotational motions in diatomic molecules, and several interesting phenomena are uncovered which would be difficult or impossible to ascertain from a spectrum alone. Nearly all aspects of the interaction between electronic and rotational motion can in fact be understood in classical terms. The thesis concludes with a discussion of ongoing work toward understanding the physical origins of the quantum defects and their dependences on molecular geometry and the electron collision energy. === by Jeffrey J. Kay. === Ph.D.