《Mechanism and rate constants for complete series reactions of 19 fluorophenols with atomic H》.pdf

JournalofEnvironmentalSciences26(2014)154-159 i 矾a onne|哦 ecc | i ： l |l ll | | i 磷目 腻sd i _ _l | l ：| 曩 薯囊 撼 链l 鬈 囊嚣 誊氇 霪萎 露誊 缓 1l w t堤-acJ l 誊| e]日目· | _ 一| 强i 曩 曩 毒叠 甓 ：羹 强 Mechanism andrateconstantsforcompleteseriesreactionsof19 fluorophenolswithatomicH RuiGao，XiaoyanSun，WanniYu，QingzhuZhang，WenxingWang EnvironmentResearchInstitute,ShandongUniversity,Jinan250100,China A R T IC L E IN F O A B ST R A C T Articlehistory： Fluorine—containinghalogenatedfluorophenolmayhaveeffectasintermediatespeciesinvolvedin Specialissue：Progressandprospects theofrmationofpolyfluorinateddibenzo-p—dioxin／dibenzofurnas(PFDDs／Fs)．Themechanism for ofatmosphericenvironmentalscience the atomic H initiated reactionswith complete seriesofnineteen fluorophenolcongenerswas inChina studiesusingthedensityfunctionaltheory．AttheMPwB1K／6—31+G(d，P)level，htegeometriesand frequenciesofreactants，transition states，nadproductswereobtained，nadhteaccurateenergetic Keywords： valueswereacquiredathteMPWB1K／6—311+G(3df,2p)leve1．Th erateconstantswereevaluatedby fluorophenols thecanonicalvariationa1rtansition．statehteory withthesmallcurvaturetunnelingcontributionover fluorophenoxyradicals awidetemperautrerna geof600L．1ooOK．Tllestudyshowshtathteintramolecularhydrogen—bondin atomicH