Ultraviolet absorption spectra and electronic structure of trialkylsilylalkanethiols

Journal Article · Mon Sep 01 04:00:00 EDT 1986 · J. Struct. Chem. (Engl. Transl.); (United States)

DOI:https://doi.org/10.1007/BF00751729· OSTI ID:6164259

Ermakov, A I; Kirichenko, E A; Makrushin, N A; Vlasova, N N; Maroshina, M Yu; Voronkov, M G

Ultraviolet absorption spectra of trialkylsilylalkanethiols R3Si(CH2)/sub n/SH (R = CH3, C2H5; n = 1-3) were obtained. The interpretation of the spectra was based on a quantum chemical calculation using a variant of the CNDO/2 method taking into account the configurational interaction of singly excited singlet states of trimethylsilylalkanethiols. Parameters were found for describing the ground state and the electronic spectra of these compounds, including the valence 3s-, 3p- and the Rydberg 3d, 4s, 4p-orbitals of sulfur in the consideration. The long-wave electronic transition in the UV spectra of trialkylsilylalkanethiols at 4.2 x 10W m is due mainly to the excitation of an electron of a p-orbital of sulfur into the virtual orbitals, including the antiboding orbitals of the Si-C bonds and the 4s-, 4p-orbitals. The subsequent electronic transition in the spectra of the compounds studied is predicted to be intravalent. The specific features of the electronic structure of trialkylsilylalkanethiols are to a certain extent due to the participation of the Rydberg 4s- and 4p-orbitals of sulfur.

• Research Organization: D.I. Mendeleev Moscow Chemical Engineering Institute, USSR
• OSTI ID: 6164259
• Journal Information: J. Struct. Chem. (Engl. Transl.); (United States), Journal Name: J. Struct. Chem. (Engl. Transl.); (United States) Vol. 27:2; 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
COMPLEXES
CONFIGURATION INTERACTION
ELECTRON SPECTROSCOPY
ELECTRONIC STRUCTURE
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXCITED STATES
HARTREE-FOCK METHOD
HYDROCARBONS
INFRARED SPECTRA
IONIZATION POTENTIAL
MATHEMATICAL MODELS
MECHANICS
MOLECULES
NITRILES
OPTIMIZATION
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
POLYATOMIC MOLECULES
QUANTUM MECHANICS
RYDBERG STATES
SELF-CONSISTENT FIELD
SILICON COMPLEXES
SPECTRA
SPECTROSCOPY
THIOLS
ULTRAVIOLET SPECTRA
VALENCE
VIBRATIONAL STATES