Ultraviolet absorption spectra and electronic structure of dialkyl sulfides

Journal Article · Thu May 01 04:00:00 UTC 1986 · J. Struct. Chem. (Engl. Transl.); (United States)

DOI:https://doi.org/10.1007/BF00748360· OSTI ID:6181510

Ermakov, A I; Makrushin, N A; Sorokin, M S; Ivanov, V S; Voronkov, M G; Kirichenko, E A

Ultraviolet spectra of solutions of dialkyl sulfides were studied in the (4.5-5.3) x 10/sup 6/ m/sup -1/ region in heptane and in acetonitrile. The experimental data obtained and the quantum-chemical calculations carried out show both the valence and the Rydberg nature of the electronic transitions observed. During the excitation of an electron in dialkyl sulfide molecules of the RSR' type, besides the inductive and steric influence of the alkyl substituents on the sulfur atom, when R = (CH/sub 3/)/sub 3-n/ CH/sub n/ (n = 0-2), there is also an interaction of the C-C bond orbitals with the p-orbitals of the sulfur atom. The substituents of dialkyl sulfides containing 3-5 and 6-10 carbon atoms, respectively, in the molecule, cause unequal interactions of their chromophore center with the solvent.

• Research Organization: D.I. Mendeleev Moscow Chemical Engineering Institute, USSR
• OSTI ID: 6181510
• Journal Information: J. Struct. Chem. (Engl. Transl.); (United States), Journal Name: J. Struct. Chem. (Engl. Transl.); (United States) Vol. 26:6; ISSN JSTCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
640302 -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ABSORPTION SPECTRA
ACETONITRILE
ALKANES
ATOMIC MODELS
CHALCOGENIDES
CHEMICAL BONDS
COMPUTERIZED SIMULATION
CONFIGURATION INTERACTION
EFFECTIVE CHARGE
ELECTRON SPECTROSCOPY
ELECTRONIC STRUCTURE
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXCITED STATES
GROUND STATES
HEPTANE
HYDROCARBONS
HYDROGEN TRANSFER
IONIZATION
IONIZATION POTENTIAL
MATHEMATICAL MODELS
MECHANICS
MOLECULES
NITRILES
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
PHOTOIONIZATION
POLYATOMIC MOLECULES
QUANTUM MECHANICS
RYDBERG STATES
SIMULATION
SPECTRA
SPECTROSCOPY
SULFIDES
SULFUR COMPOUNDS
ULTRAVIOLET SPECTRA
VALENCE