Author's School

Graduate School of Arts & Sciences

Author's Department/Program

Chemistry

Language

English (en)

Date of Award

Summer 9-1-2014

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Chair and Committee

Richard Mabbs

Abstract

In this dissertation, effects of anion excited states on photodetachment of negative ions containing transition metals will be presented. Evidence of autodetachment (sudden change in photodetachment cross section and photoelectron agular distribution) is observed for diatomic (AgF-, CuF-) and triatomic (NiO2-, CuOF-) anions. The mechanism of the autodetachment (vibrational or electronic autodetachment) is explored using ab initio calculation. EOM-CCSD calculation reveals a dipole bound anion state, which is responsible for vibrational autodetachment observed in AgF- detachment. Additionally, CAP/EOM-CCSD calculation and experimental data suggest the presence of shape resonances ([AgF-]* and [CuF-]*) which electronically autodetach to several vibrational levels of the ground state. In addition to autodetachment, photodissociation from an anion excited state is also studied. Power dependent photodetachment studies of CuO2- reveals a two photon Cu- signal for which the only isomer produced (linear OCuO-) is responsible. The dissociation pathway involves a long-lived anion excited state which is stable to electron loss but unstable to dissociation.

Comments

Permanent URL: http://dx.doi.org/10.7936/K70P0X3N

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