Effects of Anion Excited States on Photodetachment of Negative Ions

<p>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<super>-</super>, CuF<super>-</super>) and triatomic (NiO₂<super>-</super>, CuOF<super>-</super>) 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<super>-</super> detachment. Additionally, CAP/EOM-CCSD calculation and experimental data suggest the presence of shape resonances ([AgF<super>-</super>]* and [CuF<super>-</super>]*) 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<super>-</super> reveals a two photon Cu<super>-</super> signal for which the only isomer produced (linear OCuO<super>-</super>) is responsible. The dissociation pathway involves a long-lived anion excited state which is stable to electron loss but unstable to dissociation.</p>

Name thesis:degree_name

Doctor of Philosophy (PhD)

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Year dc:date.available

2014

Author dc:creator

• Dao, Diep

Contributors dc:contributor

• Richard Mabbs

• anion
• autodetachment
• dipole bound state
• photodetachment
• photoelectron imaging
• resonances

Language dc:language

English (en)

DOI

https://doi.org/10.7936/K70P0X3N

OAI identifier oai:identifier

oai:openscholarship.wustl.edu:etd-2295