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Mechanistic Investigation on the Reaction of O- with CH3CN Using Density Functional Theory
于锋, 吴琍霞, 周晓国*, 刘世林
Hefei National Laboratory for Physical Sciences at Microscale, Department of Chemical Physics, Uni-versity of Science and Technology of China, Hefei 230026, China
Abstract:
The potential energy profile of the reaction between the atomic oxygen radical anion and acetonitrile has been mapped at the G3MP2B3 level of theory. Geometries of the reactants, products, intermediate complexes, and transition states involved in this reaction have been optimized at the (U)B3LYP/6-31+G(d,p) level, and then their accurate relative energies have been improved using the G3MP2B3 method. The potential energy profile is confirmed via intrinsic reaction coordinate calculations of transition states. Four possible production channels are examined respectively, as H+ transfer, H-atom transfer, H2+ transfer, and bi-molecular nucleophilic substitution (SN2) reaction pathways. Based on present calculations, the H2+ transfer reaction is major among these four channels, which agrees with previous experimental conclusions
Key words:  Atomic oxygen radical anion, Acetonitrile, Reaction mechanism, G3MP2B3, B3LYP
FundProject:
O-与CH3CN反应机理的密度泛函理论研究
Feng Yu, Li-xia Wu, Xiao-guo Zhou*, Shi-lin Liu
中国科学技术大学合肥微尺度物质科学国家实验室,化学物理系,合肥230026
摘要:
采用G3MP2B3方法研究了氧负离子与乙腈反应的势能剖面.在(U)B3LYP/6-31+G(d,p)理论水平下分别优化了该反应势能面上反应物、产物、中间体和过渡态的分子结构,采用G3MP2B3方法校正了这些关键点的能量. 势能面上的各个反应路径均通过针对过渡态的內禀反应坐标理论计算加以确定. 分别考察了四个可能的热力学产物通道,即质子转移、氢原子转移、H2+转移和双分子亲核取代反应途径. 其中,经H2+转移生成H2O的反应通道为该反应的主要产物通道.
关键词:  氧负离子,乙腈,反应机理,G3MP2B3,B3LYP
DOI:10.1088/1674-0068/23/06/643-648
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