Experimental and Theoretical Studies of Highly-Excited Molecules at a Wide Range of Internuclear Distances
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Authors
Philippson, Jeffrey
Date
2012-01-31
Type
thesis
Language
eng
Keyword
atomic collisions , Rydberg states , laser cooling , polarimetry , molecular physics , charge transfer
Alternative Title
Abstract
Experimental and theoretical investigations of highly-excited molecules are presented
that advance the current state of knowledge of intramolecular interactions in highly-excited molecular states.
A quantitative analysis of intramolecular interactions in excited hydrogen fluoride
is presented, in which the rotational levels of the B singlet-Sigma+, v = 29 vibronic level are shown to mix with the corresponding e-parity components of the C singlet-Pi, v = 0 level. Extrapolating the experimentally-derived mixing parameter to the unperturbed limit reveals an unperturbed value of the aF hyperfine parameter of 4132(25) MHz.
Coupling energies between the ion-pair curve and long-range asymptotes of covalent states are calculated for a large number of alkali–alkali collision channels, revealing
the dependence on the internuclear distance at which the crossing takes place and
forming a foundational step for the calculation of cross-sections and rate coefficients for different charge-exchange and other processes.
To advance the experimental investigation of these systems, optical instrumentation
and associated control systems have been designed and constructed for cooling
and trapping lithium in preparation for experimental studies of cold-collisions that
will be informed by, and ultimately a test of, some of these calculated ionic–covalent
coupling energies. A novel scheme for systematic optimization of peak-locking has been developed and implemented, providing a rigorous assessment of the optimal experimental parameters. A side-of-filter offset-locking scheme was implemented,
characterizing and correcting for a previously unexplained offset in the error-signal.
A novel calibrated polarimetry scheme is demonstrated, correcting for the primary
sources of uncertainty relating to manufacturing tolerances and experimental errors. The calibrated set of polarization measurements is used to examine the purity of the optical polarization state in the light sources to be used for trapping lithium.
Description
Thesis (Ph.D, Physics, Engineering Physics and Astronomy) -- Queen's University, 2012-01-31 11:30:22.479
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