The lower-energy electronic states of a series of saturated sulfur compounds have been investigated theoretically and experimentally. The compounds investigated fell into two categories: the monosulfide series ABS in which the substituents A and B were varied, and the polysulfide series R2Sn, where n=1, 2, 3, and 4 and where R was usually CH3. The data collected included ultraviolet vapor spectra, solution spectra, solvent shifts, and vibrational data. Computations followed an approach related to that of Wolfsberg and Helmholz. This theoretical method closely approximates the experimentally observed energies in the compounds containing a single sulfur atom but encounters difficulties when two or more sulfurs are present because of the large 3dS−3dS and 4sS−4sS interactions which are predicted. It is indicated that the lower-energy excited electronic states of all the monosulfide compounds investigated are of a molecular nature in which the 4sS and 3dS atomic orbitals of sulfur play particularly dominant but by no means exclusive roles. The lower-energy excited states of the molecules R2Sn, n=2, 3, and 4, also contain significant 4s and 3d character; additionally, however, they are of S–S antibonding nature.
This d is s e rta tio n is dedicated to my parents, Mr. and Mrs. Freddie H. Watson, S r., who have done so very much for me. C ertain ly they are due much of the c re d it for the completion of th is work. ACKNOWLEDGEMENT The author would like to take th is opportunity to thank his major professor, Dr. S.P. McGlynn, whose patience, encouragement and advice made the completion of th is work p o ssib le. A sp ecial thanks is due Mrs. Falba Simmons for her encouragement and her help with the computations. Thanks are due also to the members of Dr. McGlynn1s research group for th e ir many a ssista n c e s and for many f r u i t f u l discussions; Dr. A.T. Armstrong who pioneered MO c a lc u la tio n s in these la b o ra to rie s; members of the Chemistry Department fa c u lty , e s p e c ia lly Dr. J.H. Wharton fo r many inform ative research d iscu ssio n s; the Chemistry Department s ta f f , esp e c ia lly Mr. G.H. Sexton, Mr. E. Keel and Mr. L. Dunlap; Dr. B.B. Townsend and the Computer Center s t a f f ; Dr. H.B. W illiams; Mrs. Judy Brignac and Mrs. Lynn D eSille fo r th e i r many favors and kindnesses; and Harold M. Barnes, J r. fo r his frien d sh ip. This work was supported by the Atomic Energy Commission-Biology Branch under research grant AT-(40-1)-3018. F in an c ial a ssista n c e in the p rep aratio n of th is d is s e r ta tio n was provided by the Charles E. Coates Memorial Fund,of the Louisiana State U niversity Foundation donated by George H. Coates.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.