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*,*,按一下以編輯母片標題樣式,按一下以編輯母片,第二層,第三層,第四層,第五層,*,Effect of Halogenation on the Mechanism of the Atmospheric Reactions between Methylperoxy Radicals and NO.A computational Study,作者：,Agnie M.Kosmas*,ZoiSalta,and AntonijaLesar,出處：,J.Phys.Chem.A,2009,113(15),pp 35453554,指導教授：胡維平 教授,報告學生：彭家瑜,報告日期：2010/03/29,1,Effect of Halogenation on the,Abstract,CH,3,O,2,+NO reaction had been discussed in experimental and computational studies.The authors wanted to study the influence of halogenation about this reaction by using ab initio and DFT method.The intermediate in this reaction is CHX,2,OONOcp,CHX,2,OONOtp,and CHX,2,ONO,2,.The latter one would be decomposed to CX,2,O+HONO and CHXO+XNO,2,.Halogenation stabilizes CHX,2,OONO and increases exothermicity in the overall reaction that is CHX,2,O,2,+NO CHX,2,O+NO,2,suggests that halogenation enhances the reactivity.They also discussed the ambiguous issue of CHX,2,OONO CHX,2,ONO,2,one-step isomerization and found triplet transition state in this reaction.,2,Abstract CH3O2,Outline,Introduction,Computational Methods,Results and Discussion,-RO,2,+NO,R,O+NO,2,-,ROONOtp,RONO,2,Isomerization,Conclusions,3,OutlineIntroduction3,Introduction,In Troposphere,RO,2,+NO,ROONO,R,O,+NO,2,RO,2,+NO,RONO,2,Experiment in 298K,(cm,3,mol,-1,s,-1,),CF,3,O,2,+NO,k=1.6x10,-11,CHCl,2,O,2,+NO,k=1.9x10,-11,CHBr,2,O,2,+NO,k=1.1x10,-11,CH,3,O,2,+NO,k=7.7x10,-12,Sander,S.P.;Friedl,R.R.;Golden,D.M.;Kurylo,M.J.;Moortgat,G.K.;Wine,P.H.;Ravishankara,A.R.;Kolb,C.E.;Molina,M.J.;Finlayson-Pitts,B.J.;Huie,R.E.;Orkin,V.L.Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies:Evaluation Number 15.JPL Publication 06-2;National Aeronautics and Space Administration,Jet Propulsion Laboratory,California Insitute of Technology:Pasadena,CA,2006.,Sehested,J.;Nielsen,O.J.;Wallington,T.J.,Chem.Phys.Lett,.,1993,213,457,Reduction of the RO-O bond strength,4,IntroductionIn TroposphereSand,Introduction,Computational Studies,CHCl,2,O,2,is,more reactive related to CH,3,O,2,+NO,RO,2,+NO,ROONO,RO,2,+NO,RONO,2,R=alkyl group,ROONO,RONO,2,isomerization,King,M.D.;Thomson,K.C.,Atmos.Environ,.,2003,37,4517,Lohr,L.L.;Barker,J.R.;Stroll,R.M.,J.Phys.Chem.A,2003,107,7429,Zhao,Y.;Houk,K.N.;Olson,L.P.,J.Phys.Chem.A,2004,108,5864,Barker,J.R.;Lohr,L.L.;Stroll,R.M.;Reading,S.,J.Phys.Chem.A,2003,107,7434,Zhang,J.;Dransfield,T.;Donahue,N.M.,J.Phys.Chem.A,2004,108,9082,Zhang,J.;Dransfield,T.;Donahue,N.M.,J.Phys.Chem.A,2004,108,9082,Zhao,Y.;Houk,K.N.;Olson,L.P.,J.Phys.Chem.A,2004,108,5864,5,IntroductionComputational Stud,Computational method,Method,Geometry and vibrational frequencies：(U)MP2、(U)B3LYP,Single-point energies：CCSD(T),Mutilevel：G2(MP2)、G3/B3LYP,Basis set,6-311+G(d,p),Program,Gaussian 03,6,Computational methodMethod6,Results and Discussion,The Mechanism of CHX,2,O,2,+NO,CHX,2,O,2,+NO,CHX,2,OONO,CHX,2,O+NO,2,CHX,2,ONO,2,CHX,2,O+NO,2,CHX,2,ONO,2,CX,2,O+HONO,CHX,2,ONO,2,CHXO+X,NO,2,The Halogenation,X=H、F、Cl,7,Results and DiscussionThe Mech,Energy profile,CHX,2,O,2,+NO,CHX,2,OONOcp,CHX,2,OONOtp,TS cp-tp,CHX,2,O+NO,2,G3/B3LYP,8,Energy profileCHX2O2+NOCHX2OON,-MP2,-B3LYP,(halogenated methyl peroxynitrite),9,-MP2(halogenated methyl peroxy,Results and Discussion,a,Relative energy(kcal/mol)respect to CHX,2,O,2,+NO,b,The energy including zero-point energy,10,Results and Discussiona Relati,Energy profile,CHCl,2,O,2,+NO,CHCl,2,OONOcp,CHCl,2,OONOtp,TS cp-tp,CHCl,2,O+NO,2,CHCl,2,ONO,2,CClHO+ClNO,2,CCl,2,O+HONO,TS ccl,2,o,TS cclho,G3/B3LYP,11,Energy profileCHCl2O2+NOCHCl2O,(halogenated,methyl nitrate),-MP2,-B3LYP,12,(halogenated methyl nitrate)-M,Energy profile,CHCl,2,O+NO,2,CHCl,2,ONO,2,TS ccl,2,o,TS cclho,CClHO+ClNO,2,CCl,2,O+HONO,CHF,2,O+NO,2,CHF,2,ONO,2,TS cf,2,o,TS cfho,CFHO+FNO,2,CF,2,O+HONO,G3/B3LYP,13,Energy profileCHCl2O+NO2CHCl2O,Results and Discussion,a,Relative energy(kcal/mol)respect to CHX,2,O,2,+NO,b,The energy include zero-point energy,14,Results and Discussiona Relati,Experimental Results(IR spectra),Chiappero,M.S.;Burgos Paci,M.A.;Arg ello,G.A.;Wallington,T.,J.Inorg.Chem,.,2004,43,2714,CHF,2,O,2,NO,2,+h,CHF,2,ONO,2,CHF,2,ONO,2,CFHO+FNO,2,CHF,2,ONO,2,(80 10%),CFHO(1020%),15,Experimental Results(IR spect,Results and Discussion,Bond distances(,),16,Results and DiscussionBond dis,Results and Discussion,ROONOtp,RONO,2,Experimental results,RO,2,+NO,RONO,2,RO,2,+NO,RO+NO,2,RONO,2,(low pressure),Computational results,RO,2,+NO,ROONO,R,O+NO,2,RONO,2,(low pressure),RO,2,+NO,ROONOtp,RONO,2,(moderate&high pressure),Arey,J.;Aschmann,S.M.;Kwok,E.S.C.;Atkinson,R.,J.Phys.Chem.A,2001,105,1020,Lesar,A.;Hodo ek,M.;Drougas,E.;Kosmas,A.M.,J.Phys.Chem.A,2006,110,7898,17,Results and DiscussionROONOtp,B3LYP/6-311+(d,p),Potential Energy Curve,2006,18,B3LYP/6-311+(d,p)Potential En,Results and Discussion,a,Relative energy(kcal/mol)respect to CHX,2,O,2,+NO,b,The energy including zero-point energy,19,Results and Discussiona Relati,Experimental Result,At near room temperature and 1atm,CF,3,O,2,+NO produce at least 3 times more,CX,3,ONO,2,than CH,3,O,2,+NO.,C