高等学校化学学报
高等學校化學學報
고등학교화학학보
CHEMICAL JOURNAL OF CHINESE UNIVERSITIES
2014年
5期
1023-1028
,共6页
l-Cn H自由基%反应机理%氧化%氧迁移
l-Cn H自由基%反應機理%氧化%氧遷移
l-Cn H자유기%반응궤리%양화%양천이
l-Cn H radical%Reaction mechanics%Oxidation%Oxygen transfer
为了探索更长的碳链自由基l-CnH与O2反应的机理,在CCSD(T)/CC-PVTZ+ZPVE//B3LYP/6-311++G(d,p)的计算水平下,讨论了当n=5,6时, l-CnH+O2的各个异构化反应通道。当n=5时,主要反应通道为碳迁移过程,生成主要产物为P2(CO2+C4H)；当n=6时,碳-氧交换[产物为P1(CO+HC5O)]和氧迁移过程[产物为P3(3O+HC6O)]均为主要通道,并具有很高的竞争性。将所得结构与l-CnH(n≤4)+O2的反应机理进行了对比。
為瞭探索更長的碳鏈自由基l-CnH與O2反應的機理,在CCSD(T)/CC-PVTZ+ZPVE//B3LYP/6-311++G(d,p)的計算水平下,討論瞭噹n=5,6時, l-CnH+O2的各箇異構化反應通道。噹n=5時,主要反應通道為碳遷移過程,生成主要產物為P2(CO2+C4H)；噹n=6時,碳-氧交換[產物為P1(CO+HC5O)]和氧遷移過程[產物為P3(3O+HC6O)]均為主要通道,併具有很高的競爭性。將所得結構與l-CnH(n≤4)+O2的反應機理進行瞭對比。
위료탐색경장적탄련자유기l-CnH여O2반응적궤리,재CCSD(T)/CC-PVTZ+ZPVE//B3LYP/6-311++G(d,p)적계산수평하,토론료당n=5,6시, l-CnH+O2적각개이구화반응통도。당n=5시,주요반응통도위탄천이과정,생성주요산물위P2(CO2+C4H)；당n=6시,탄-양교환[산물위P1(CO+HC5O)]화양천이과정[산물위P3(3O+HC6O)]균위주요통도,병구유흔고적경쟁성。장소득결구여l-CnH(n≤4)+O2적반응궤리진행료대비。
The CnH free radicals were reported to play an important role in interstellar chemistry. The oxida-tion processes of CnH radicals with n=1—4 had been explored by means of the theoretical and experimental methods. To further understand the reaction properties of the long carbon chain radicals, we report the first theoretical survey of the l-C5H+O2 and l-C6H+O2 reactions at the CCSD(T)/CC-PVTZ+ZPVE//B3LYP/6-311++G( d,p) level. The carbon transfer was found to be the main pathway in the l-C5 H+O2 reaction, giving the main product P2( CO2+C4 H) . Yet, the case is a little different for l-C6 H+O2 . The energy barrier between the C,O-exchange[resulting in P1(CO+HC5O)] and the oxygen transfer[resulting in P3(3O+HC6O)] is only 0. 4 kJ/mol, indicative of their co-predominance. The present results were compared with the shorter l-CnH radicals with O2.
