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Date of Award
5-2010
Access Type
Campus Access
Document type
dissertation
Degree Name
Doctor of Philosophy (PhD)
Degree Program
Chemistry
First Advisor
Howard D. Stidham
Second Advisor
Ricardo Metz
Third Advisor
Edward Voigtman, Jr.
Subject Categories
Analytical Chemistry | Physical Chemistry
Abstract
Ab initio calculations were utilized to demonstrate the theory behind molecular properties and were correlated to actual spectroscopic results in the infrared and Raman. Symmetrical aspects of small flexible molecules were examined to determine how symmetry coordinates mix in the potential energy distribution and whether these are infrared and Raman active.
The difficulty is the spectroscopic landscape of the spectrum gets extremely complicated even in very small carbon chain dihalides. The example of 1,4-dichlorobutane is provided. The work here will provide a solid reference for future research as we have found in previous work that 1,2-dibromopropane, a sensitive compound, has in previous publications shown what looks to be degradation. Three other publications are in preparation allyldichlorosilane, n-butylgermane and n-butylsilane of which the two finial compounds have conformers with the same symmetry.
Instrumentation has been updated to be continually maintained and upgraded to be viable and competitive. Times for crystallizations of spectroscopic compounds for the IR and Raman cold cells can exceed 50-60 hours of continuous annealing. Modification and development of equipment allowed a level of automation and a much more precise temperature control at lower temperatures that would not have been possible before.
DOI
https://doi.org/10.7275/5670372
Recommended Citation
LaPlante, Arthur James, "Vibrational Spectrum, Ab Initio Calculations, Conformational Stabilities And Assignment Of Fundamentals Of Small Flexible Molecules" (2010). Doctoral Dissertations 1896 - February 2014. 180.
https://doi.org/10.7275/5670372
https://scholarworks.umass.edu/dissertations_1/180