Scaled Hartree-Fock force field calculations for organothallium compounds: Normal-mode analysis for TlCH sub 3 Tl(CH sub 3 ) sub 2 sup + , Tl(CH sub 3 ) sub 3 , Tl(CH sub 3 ) sub 2 Br, and Tl(CH sub 3 ) sub 4 sup minus

In a recent paper we presented Hartree-Fock (HF) calculations for aliphatic organothallium compounds. The diagonal HF force constants obtained from a Fletcher-Powell geometry optimization are now used for a normal-mode analysis of TlCH{sub 3}, Tl(CH{sub 3}){sub 2}{sup +}, Tl(CH{sub 3}){sub 3}, Tl(CH...

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Bibliographic Details
Published in:Organometallics 1990-02, Vol.9:2
Main Authors: Schwerdtfeger, P., Bowmaker, G.A., Boyd, P.D.W., Ware, D.C., Brothers, P.J., Nielson, A.J.
Format: Article
Language:English
Subjects:
360104 - Metals & Alloys- Physical Properties
400200 - Inorganic, Organic, & Physical Chemistry
CALCULATION METHODS
DATA
DATA ANALYSIS
EQUATIONS
EXPERIMENTAL DATA
FIELD EQUATIONS
HARTREE-FOCK METHOD
INFORMATION
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
MATERIALS SCIENCE
MATHEMATICAL MODELS
MEASURING INSTRUMENTS
MEASURING METHODS
NORMAL-MODE ANALYSIS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
THALLIUM COMPOUNDS
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Summary:In a recent paper we presented Hartree-Fock (HF) calculations for aliphatic organothallium compounds. The diagonal HF force constants obtained from a Fletcher-Powell geometry optimization are now used for a normal-mode analysis of TlCH{sub 3}, Tl(CH{sub 3}){sub 2}{sup +}, Tl(CH{sub 3}){sub 3}, Tl(CH{sub 3}){sub 2}Br, and Tl(CH{sub 3}){sub 4}{sup {minus}}. In order to calculate frequencies comparable to experimental values, the HF force field has been scaled by using scaling factors obtained from experimental infrared and Raman measurements on Tl(CH{sub 3}){sub 2}{sup +} and TlBr. The vibrational spectra of Tl(CH{sub 3}){sub 2}{sup +} were remeasured (infrared and Raman) in order to obtain an accurate force field. Predictions are made for the vibrational spectrum of the as yet undetected TlCH{sub 3} molecule. Experimental infrared and Raman results for Tl(CH{sub 3}){sub 3} compare reasonably well with our calculated frequencies. Relativistic and correlation effects are analyzed for the vibrational frequencies of Tl(CH{sub 3}){sub 2}{sup +}.
ISSN:0276-7333
1520-6041
DOI:10.1021/om00116a030