标题：Theoretical investigation of the oxidation pathways of the Cl-initiated reaction of 2-methyl-3-buten-2-ol
作者：Zhang, W.;Zhang, D.
作者机构：[Zhang, W] Key Laboratory of Colloid and Interface Chemistry, Institute of Theoretical Chemistry, Shandong University, Jinan 250100, China, College of 更多
通讯作者地址：[Zhang, DJ]Shandong Univ, Inst Theoret Chem, Minist Educ, Key Lab Colloid & Interface Chem, Jinan 250100, Peoples R China.
关键词：2-methyl-3-buten-2-ol;CCSD(T);Cl atoms;reaction mechanism
摘要：The mechanism and products of the reaction of 2-methyl-3-buten-2-ol (MBO232) with Cl atoms in the presence of O2 have been elucidated by performing high-level quantum chemistry calculations. The geometries of the reactants, intermediates, transition states, and products are optimized at the MP2(full)/6-311G(d,p) level, and their single-point energies are refined at the CCSD(T)/6-311+G(d,p) level. The potential energy surface profiles have been constructed at the CCSD(T)/6-311+G(d,p)//MP2(full)/6-311G(d,p)+0.95ZPE level of theory, and the possible channels involved in the reaction are also discussed. The calculations indicate that the reaction predominantly proceeds via the addition of Cl atoms to the double bond rather than the direct abstraction of the H atoms in MBO232. The nascent adducts (CH_3)2C(OH) CHCH_2Cl (IM1) and (CH_3)_2C(OH)CHClCH_2 (IM2) do not undergo subsequent isomerization and dissociation reactions, but rather react with O2. The theoretical results show that the major products are CH2ClCHO and CH_3C(O)CH_3 for the reaction of MBO232+Cl in the presence of O2, which is in good agreement with the experimental finding.