Comparative analysis of electronic states of saturated dioxa and dithia heterocycles and their radical cations

Journal Article · Thu Oct 22 04:00:00 EDT 1987 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100306a018· OSTI ID:5795143

Momose, T; Tanimura, R; Ushida, K; Shida, T

ESR spectra of the radical cations of 1,3-dioxa- and 1,3-dithiacyclopentanes and their 2-methylated derivatives were studied both experimentally and theoretically. The orbital interaction analysis based on the localized orbital indicates that the order of the two highest occupied molecular orbitals is reversed between the dioxa and the dithia systems. It is concluded that the reversal is caused by the interaction of the orbital localized on the methylene C-H bonds of carbon atom 2 with the out-of-plane lone-pair MO composed of the lone-pair orbitals on the oxygen and the sulfur atoms. The use of the usual canonical orbital and the internally consistent SCF orbital proposed by Davidson as the base is discussed comparatively.

• Research Organization: Kyoto Univ., Japan
• OSTI ID: 5795143
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 91:22; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
ALKANES
ATOMIC MODELS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
CHLORINATED ALIPHATIC HYDROCARBONS
CYCLOALKANES
DATA
DECOMPOSITION
ELECTRON SPIN RESONANCE
EXPERIMENTAL DATA
FLUORINATED ALIPHATIC HYDROCARBONS
HALOGENATED ALIPHATIC HYDROCARBONS
HYDROCARBONS
INFORMATION
LOW TEMPERATURE
MAGNETIC RESONANCE
MATHEMATICAL MODELS
MOLECULAR ORBITAL METHOD
MOLECULES
NUMERICAL DATA
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIOLYSIS
RESONANCE