Role of the electrons in inner valence MO's displayed in the x-ray photoelectron spectrum of the F/sub 2/ molecule in its chemical bond (in Russian)
The results of a quantum-chemical calculation of the electronic structure of the F/sub 2/ molecule by the CNDO/2 and X..cap alpha..-SW methods have been presented. The binding energies of the valence electrons calculated in accordance with Slater's transition-state principle are in quantitative agreement with the experimental x-ray photoelectron data. The bonding character of the MO's have been evaluated on the basis of a calculation of the derivatives of the binding energy with respect to the internuclear distance and by determining the values of the orbital resonance energies, which characterize the covalent contribution of the electrons in different MO's to the chemical bonding in the molecule. It has been shown that the electrons in the inner valence 2sigma/sub g/ MO make a significant contribution to the bonding of the atoms, which is only partially compensated by the antibonding properties of the 2sigma/sub u/* inner valence MO. The predominant participation of the 2s AO's of the fluorine atoms in the formation of the 2sigma/sub g/ and 2sigma/sub u/* inner valence MO's has been established and is the reason for their significant stabilization and smaller energy splitting in comparison of other diatomic molecules, for example, N/sub 2/. The specific feature of these MO's determine the clearly expressed bonding character of the 3sigmag MO, which is caused by the predominant interaction of the fluorine 2psigma AO.
- Research Organization:
- Institute of Fossil Fuels, Moscow, USSR
- OSTI ID:
- 6136332
- Journal Information:
- Theor. Exp. Chem. (Engl. Transl.); (United States), Vol. 21:2; Other Information: Translated from Teor. Eksp. Khim.; 21: No. 2, 211-217(Mar-Apr 1985)
- Country of Publication:
- United States
- Language:
- Russian
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
FLUORINE
ATOMIC MODELS
BINDING ENERGY
ELECTRONIC STRUCTURE
HYPERFINE STRUCTURE
X-RAY SPECTRA
CHEMICAL BONDS
CONFIGURATION INTERACTION
ELECTRONS
EXCITED STATES
GROUND STATES
INNER-SHELL IONIZATION
INTERATOMIC DISTANCES
PHOTOIONIZATION
QUANTUM MECHANICS
SELF-CONSISTENT FIELD
SLATER METHOD
VALENCE
DISTANCE
ELEMENTARY PARTICLES
ELEMENTS
ENERGY
ENERGY LEVELS
FERMIONS
HALOGENS
IONIZATION
LEPTONS
MATHEMATICAL MODELS
MECHANICS
NONMETALS
SPECTRA
400201* - Chemical & Physicochemical Properties
640302 - Atomic
Molecular & Chemical Physics- Atomic & Molecular Properties & Theory