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Title: Vibronic coupling in light diatomic molecules : the hydrogen halides
Author: McFadyen, Gordon G.
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1991
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The electronic spectroscopy of the hydrogen halides has been investigated using laser multiphoton excitation techniques; the (2+ 1)REMPI spectra of HBr, DBr, and HI in the two-photon energy range 76000 - 83000 cm-1 and 67000 - 73000 cm-1, the fluorescence excitation spectra of DCl and HI, and the fluorescence emission from ion-pair and Rydberg states in HCl, DCl, and HI have been recorded. New transitions were observed in the (2+ 1)REMPI spectra of HBr, DBr, and HI and a previously reported transition in HBr was reassigned. The fluorescence spectra recorded from a number of 0+ Rydberg states in HCl, DCl, and HI showed structure characteristic of the ion-pair state which indicates that these states vibronically couple with the ion-pair state. In HCl and DCl the g3Σ- (0+ ) and E+ (0+ ) Rydberg states are coupled to the ion-pair state while in HI the E+ (0+ ) and j3Σ- (0+ ) Rydberg states are coupled to the ion-pair state. Numerical modelling techniques were used in the analysis of both the previously reported spectra and the experimental results presented herein. The excited states and the coupling between them were modelled in both the diabatic and adiabatic representations. The vibrational energy levels and rotational constants have been calculated and the absorption and fluorescence spectra of HCl and DCl have been simulated. The comparison of observed and calculated data has been used to refine the model of the potential curves and the coupling between the states. The greatest amount of information was available for HCl and so the work reported here has concentrated on this molecule and DCl.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available