Year of Publication

2014

Degree Name

Doctor of Philosophy (PhD)

Document Type

Doctoral Dissertation

College

Arts and Sciences

Department

Chemistry

First Advisor

Dr. Dennis Clouthier

Abstract

Radicals are interesting to study because of importance in so many processes such as semiconductor growth or stellar evolution. Laser induced fluorescence (LIF) and wavelength resolved emission spectra of jet cooled HPS, HAsO, AsD2, H2PS, and F2BO have been measured using the pulsed discharge jet technique.

Several bands in the à 1A′′ − X̃ 1A′ transition of HPS were observed and assigned with the help of ab initio calculations. The ab initio geometries showed that HPS does not follow Walsh’s predictions for the angle change upon electronic excitation; Walsh predicts an increase in HPS upon excitation while a decrease is calculated. Ab initio Walsh-style orbital angular correlation diagrams for both electronic states show a change in correlation for some orbitals upon electronic excitation, an effect that Walsh did not predict.

The à 1A′′ − X̃ 1A′ transitions were measured in HAsO and DAsO for the first time. A molecular geometry was derived for each electronic state from experimental rotational constants. The experimental geometries prove that HAsO also violates Walsh’s rules for the same reason shown in HPS.

The à 2A1 – X̃ 2B1 electronic transition of AsD2 and AsHD were measured. Vibrational levels observed in emission were fit to a local mode vibrational Hamiltonian. Using the previously reported rotational constants for AsH2 and those determined for AsD2 in this work, an improved estimate of the excited state geometry was obtained.

The discovery of the B̃ 2A′ − X̃ 2A′ band system of H2PS is the first report of this molecule. Both D2PS and HDPS were also observed. Ab initio calculations helped assign the transition. H2PS is one of the few tetra-atomic or larger molecules that violates Kasha’s empirical rule due to the large separation between the B̃ and à states.

Finally, laser induced fluorescence spectra of the F2BO radical was observed for the first time. Previous work showed two band systems with only a tentative assignment. The measured LIF spectra confirm the identity of the two band systems as the B̃ 2A1 – X̃ 2B2 and the B̃ 2A1 – Ã 2B1 transitions showing F2BO also violates Kasha’s rule.

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