An investigation of the electronic spectra of a series of organic sulfur compounds

Technical Report · Sun Aug 01 04:00:00 UTC 1965

OSTI ID:6877154

Thompson, S D

Purpose of this study was to experimentally determine the energy of the first few excitations in a series of saturated sulfur compounds (..pi..-electron systems), gather empirical data that would aid in their assignments, and obtain a theoretical treatment that would predict the energies and nature of the transitions. The series of compounds selected for investigation fell into two groups: in the first group the attached substituents were varied; in the second group the number of sulfur atoms in the chain was varied. The empirical data collected included ultraviolet vapor spectra, solvent effects on spectra and vibrational data. Computations were performed on all compounds following an approach closely related to that of Wolfsberg and Helmholz. A free electron treatment was applied to predict the energies of the long wavelength transition in polysulfides. The Wolfsberg-Helmholz type treatment closely approximates the experimentally observed energies in the compounds containing a single sulfur atom but encounters difficulties when two or more sulfurs are present due to large predicted 3d/sub S/-3d/sub S/ interactions. However, treatment of the long wavelength absorption in the polysulfides as an n ..-->.. 4s/sub S/ transition by the free electron method yields good results. The calculations indicate that the first several transitions in all of the compounds investigated are to low-lying perturbed Rydberg levels. A study was conducted into photolysis of cyclic disulfides. Under one set of conditions the photolysis proceeds by -S-S- scission while under a different set of conditions the initial step is C-S scission.

• Research Organization: Louisiana State Univ., Baton Rouge (USA)
• DOE Contract Number: AS05-76EV03018
• OSTI ID: 6877154
• Report Number(s): DOE/EV/03018-T10; ON: DE87007132
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHALCOGENIDES
CHEMICAL REACTIONS
DECOMPOSITION
ENERGY-LEVEL TRANSITIONS
HYDROGEN COMPOUNDS
HYDROGEN SULFIDES
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
SPECTRA
SULFIDES
SULFUR COMPOUNDS
THIOLS