Theoretical study of reactivity of methane, methyl fluoride, and methyl chloride: Interaction with their radical cations and proton donors

Journal Article · Wed Jul 18 04:00:00 EDT 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00171a009· OSTI ID:6812109

Hess, Jr, B A ^[1]; Zahradnik, R ^[2]

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1. Vanderbilt Univ., Nashville, TN (USA)
2. J. Heyrovsky Institute, Prague (Czechoslovakia)

This work deals with interactions between CH{sub 4} and CH{sub 4}{sup {sm bullet}+}, CH{sub 3}F and CH{sub 3}F{sup {sm bullet}+}, and CH{sub 3}Cl and CH{sub 3}Cl{sup {sm bullet}+}. The calculated {Delta}H{sub 0} values (MP4/6-31G**//MP2/6-31G**, ZPE included) for processes leading to CH{sub 5}{sup +} and CH{sub 3}{sup {sm bullet}}, and to CFH{sub 4} and CH{sub 2}F{sup {sm bullet}} amount to {minus}1.8 and {minus}21.0 kcal/mol, respectively. The {Delta}H{sub 0} leading to CClH{sub 4}{sup +} and CH{sub 2}Cl{sup {sm bullet}} (MP4/6-31G**//SCF/6-31G**, ZPE included) is {minus}2.3 kcal/mol. The calculated reaction heat for the first interaction is significantly closer to experimental values ({minus}4.16 and {minus}6 kcal/mol, respectively) than their previous theoretical estimates. The structures of the radical cations (CH{sub 4}{sup {sm bullet}+}, CH{sub 3}F{sup {sm bullet}+}) possess features of van der Waals associates.

• OSTI ID: 6812109
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:15; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKANES
CALCULATION METHODS
CATIONS
CHARGED PARTICLES
CHLORINATED ALIPHATIC HYDROCARBONS
COLLISIONS
DATA ANALYSIS
FLUORINATED ALIPHATIC HYDROCARBONS
HALOGENATED ALIPHATIC HYDROCARBONS
HYDROCARBONS
ION COLLISIONS
ION-MOLECULE COLLISIONS
IONS
MATHEMATICAL MODELS
METHANE
METHYL CHLORIDE
METHYL FLUORIDE
MOLECULE COLLISIONS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
REACTIVITY