THEORETICAL STUDY ON THE MECHANISM OF THE CH3OH + •XH3 (X = C, Si) REACTIONS

Authors: Nguyễn Trọng Nghĩa*, Nguyễn Ngọc Tuệ

Abstract

The mechanism for the reactions of methanol (CH3OH) with •XH3 (X = C, Si) radicals have been investigated by ab initio molecular orbital theory based on the CCSD(T)//B3LYP/aug-cc-pVTZ method. For the CH3OH + •CH3 reaction, the major product pathways channels are H-abstraction forming PR1 (CH3O• +CH4: 0,0 kcal.mol-1) and PR2 (•CH2OH + CH4: -8,1 kcal.mol-1) via transition states TS1 and TS2 lying 12,0 and 12,8 kcal/mol above the reactants, respectively. While for the CH3OH + •SiH3 reaction, the major product pathways channels are the H-abstraction forming PR7 (•CH2OH + SiH4: 3,4 kcal/mol) and substitution channels forming PR8 (H• + CH3OSiH3: -0,3 kcal.mol-1) and PR9 (•CH3 + SiH3OH: -28,7 kcal.mol-1) via transition states TS7 (16,2 kcal.mol-1), TS8 (16,5 kcal.mol-1) and TS9 (17,0 kcal.mol-1), respectively. The predicted geometry parameters for the species in the PESs and the heats of reaction in this work are in good agreement with available experimental data.

Keyword

Reaction mechanism, silyl radical (•SiH3), methyl radical (•CH3), methanol (CH3OH), PES
Pages : 73-78

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