標題: Anharmonic Effect of the Unimolecular Isomerization/Decomposition of Benzyne
作者: Li, Qian
Yao, Li
Lin, S. H.
應用化學系
Department of Applied Chemistry
關鍵字: Anharmonic effect;Unimolecular reaction;Rate constant;Rice-Ramsperger-Kassel-Marcus (RRKM) theory
公開日期: 1-四月-2015
摘要: The anharmonic and harmonic rate constants were calculated for the unimolecular decomposition of o-benzyne, the isomerization of o-benzyne to m-benzyne, the isomerization of m-benzyne to p-benzyne and unimolecular decomposition of p-benzyne by using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory respectively, in the canonical and microcanonical systems. The geometry and the vibrational frequencies were calculated by MP2 and B3LYPmethods with 6-311G(d,p) basis set and the barrier energies were corrected using CBS-QB3 theory. The anharmonic effect on the reactions was also examined. Comparison of results for the decompositions of benzyne indicate that both in microcanonical and canonical cases, the anharmonic effect on the decomposition of the o-C6H4 and p-C6H4 are significant, while the anharmonic effect on the two isomerizations are not pronounced.
URI: http://dx.doi.org/10.1002/jccs.201400345
http://hdl.handle.net/11536/124703
ISSN: 0009-4536
DOI: 10.1002/jccs.201400345
期刊: JOURNAL OF THE CHINESE CHEMICAL SOCIETY
Volume: 62
起始頁: 355
結束頁: 365
顯示於類別:期刊論文