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《OH^-与CH_2ClF反应的阴离子产物通道.pdf》由会员上传分享,免费在线阅读,更多相关内容在行业资料-天天文库。
1、物理化学学报(WuliHuaxueXuebao)AprilActaPhys.一Chim.Sin.2011,27(4),801-807801[Article]www.whxb.pku.edu.caOH一与CH2CIF反应的阴离子产物通道宋磊’于锋吴刑霞周晓国刘世林’(合肥微尺度物质科学国家实验室(筹),中国科学技术大学化学物理系,合肥230026;西安工业大学数学物理系,西安710032)摘要:理论研究了羟基负离子(OH一)与氟氯代甲烷(CHCIF)反应的阴离子产物通道.分别在B3LYP/6—31+G(d,p)和B3LYP/6.311++G(2d,p)水平上得到反
2、应势能面上各关键物种的优化构型,进而计算得到谐振频率和零点能.基于CCSD(T)/6.311+G(3dr,3dp)水平的相对能量,描述了由质子转移和双分子亲核取代(S2)过程生成各阴离子产物的途径.各阴离子产物途径势垒的计算结果表明质子转移过程是实验中的主要产物通道,与以往实验测量的结论相符.此外,计算还显示双分予亲核取代过程得到了非典型的阴离子产物,其中动力学效应可能会导致F一的生成.关键词:羟基负离子:氟氯代甲烷:反应机理:质子转移:亲核取代(S2)反应中图分类号:O641AnionicProductionPathwaysInvolvedintheReact
3、ionbetweenOH—andCH2CIFSONGLei’YUFengWULi—Xia’ZHOUXiao—Guo’LIUShi—Lin’(HefeiNationalLaboratoryyorPhysicalSciencesattheMicroscale,DepartmentofChemicalPhysics,UniversityofScienceandTechnologyofChina,Hefei230026,R.China;2DepartmentofMathematicsandPhysics,XianTechnologicalUniversity,Xian7
4、10032,R.China、Abstract:Theanionicproductionpathwaysinvolvedinthereactionbetweenhydroxideanion(OH一1andchlorofluoromethane(CH2CIF)weretheoreticallyinvestigated.TheoptimizedgeometriesofaltheimportantspeciesonthereactionpotentialenergysurfacewereobtainedattheB3LYP/6—31+G(d,P)andB3LYP/6—3
5、11++G(2d,P)levels.Consequently,harmonicvibrationalfrequenciesandzeropointenergies(ZPEs)werecalculated.BasedontherelativeenergiesofalIthespeciesthatwerecalculatedattheCCSD(T)/6—311+G(33dlp)Ievel,theanionicproductionchannelsfortheH-abstractionandthebimolecularnucleophilicsubstitutionfS
6、N2)reactionprocessesareelaboratedupon.ACCOrdingtothecalculatedbarrierheightsfortheproductionpathways,theHabstractionchannelisdominant,whichagreesverywelwithpreviousexperimentalconclusions.Inaddition.Don—typicalanionicproductsaresuggestedtof0rmduringtheSN2reactionprocesseswheretheseri
7、ousdynamicefectprobablycausestheSN2reactionprocesstoproduceF一.KeyWords:Hydroxideanion;Chlorofluoromethane;Reactionmechanism;Protontransfer;Nucleophilicsubstitution(SN2)reactionReceived:November24,201O:Revised:January24,201l:PublishedonWeb:March2,2011.Correspondingauthor.Email:xzhou@u
8、stc.edu.cn;T
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