High resolution spectroscopy of scandium monohalides

Abstract

This thesis reports the study of the molecular and electronic structure of scandium monohalides using the technique of laser ablation/reaction with supersonic free jet expansion used for producing the target molecules and laser induced fluorescence (LIF) spectroscopy for recording their electronic transition spectrum. The scandium diatomic molecules studied in this work were scandium monoiodide (ScI) and scandium monobromide (ScBr), which were produced by the reaction of Sc atoms with 2% CH3I and 2% C2H5Br gases seeded in Ar carrier gas, respectively. The LIF spectrum of the electronic transition of ScI and ScBr were recorded in the visible and near infrared spectral region between 613 and 854 nm. The analysis of the high resolution electronic spectra of ScI and ScBr yielded molecular constants and information of electronic structures. For all the transition bands observed, rotationally-resolved transition lines were fit to a theoretical model to retrieve molecular constants for both upper and lower electronic states.

For the ScI molecule, seven vibrational bands of the D1П –X^1 Σ^+ system were recorded and analyzed. Accurate molecular constants for the v = 0 – 2 levels of the D^1П state and the v = 0 – 3 levels of the X^1 Σ^+ state were obtained. The equilibrium bond lengths, re (Å), for the electronic states of ScI were determined as follows:

ScI X^1 Σ^+ D^1П r_e(Å) 2.6078 2.7146

For the ScBr molecule, three electronic transition systems were recorded and analyzed, which include six vibrational bands of the C^1 Σ^+– X^1 Σ^+ system, seven vibrational bands of the e^3Δ–a^3Δsystem and two vibrational bands of the d3Φ – a3Δ system. Rotationally resolved transition lines of both Sc79Br and Sc81Br isotopes were observed and analyzed. Least-squares fitting of the measured line positions yielded accurate molecular constants for the v = 0 – 2 levels of the X^1 Σ^+ state, the v = 0 – 3 levels of the C^1 Σ^+ state, the v = 0 and 1 levels of the d3Φ state and the v = 0 – 2 levels of both e3Δ and a3Δ states, respectively. The equilibrium bond lengths, re (Å), determined for electronic states of ScBr are given as follows:

ScBr X^1 Σ^+ a^3Δ C^1 Σ^+ r_e(Å) 2.3806 2.4767 2.4776

A molecular orbital (MO) energy level diagram has been used to examine the electronic configurations giving rise to the different observed electronic states of ScI and ScBr. An attempt has been made to put the MOs of all the scandium monohalides under a single picture. A comparison of the molecular constants for the different electronic states of scandium monohalides indicates a weakening of the chemical bonding between the scandium atom and the halogen atoms down the group.