NO_2和HSO反应的机理及动力学研究
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摘要
本文采用CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ方法构建了NO_2+HSO反应的单、三重态势能面,并对主通道速率常数进行了计算。结果表明,该反应在单[R1(HN(O)O+~1SO)、R2 (cis-HONO+~1SO)和R3 (trans-HONO+~1SO)]、三重态[R6 (HN (O)O+~3SO)、R7 (cis-HONO+~3SO)和R8 (trans-HONO+~3SO)]均存在3条抽氢反应通道,在单[R4(NO+HS(O)O)和R5(H+SO_2+NO)]、三重态[R9(HS(O) O+NO)和R10(H+SO_2+NO)]均存在两条抽氧通道,其中单重态抽氢通道R2(cis-HONO+~1SO)是NO_2+HSO反应主通道。利用传统过渡态理论(TST)并结合Wigner校正,计算了上述10条通道在200K～1000K温度范围内的速率常数。计算结果表明,NO_2+HSO反应主通道在298K时的速率常数(7.78×10-13cm3·molecule-1·s-1)与实验值(9.6×10-12cm3·molecule-1·s-1)相近。此外,水分子影响主通道R2(cis-HONO+~1SO)经历了NO_2+H_2O…HSO和NO_2+H_2O…HSO(HSO+NO_2…H_2O)两条反应通道,且两条通道的能垒分别比R2升高了49.97和20.67 kcal·mol-1,说明在实际大气环境中水分子对NO_2+HSO反应几乎没有影响。
The mechanism for the reaction between NO_2 and HSO was investigated at the CCSD(T)/aug-ccp VTZ//B3 LYP/aug-cc-pVTZ level on both the singlet and triplet potential energy surfaces(PESs).The results showed that there are three hydrogen abstraction reaction channels on both singlet [R1 HN(O) O+~1SO),R2(cisHONO+~1SO),and R3(trans-HONO+~1SO)] and triplet [R6(HN(O) O +~3SO),R7(cis-HONO +~3SO),and R8(trans-HONO+~3SO)] PESs,as well as two oxygen abstraction reaction channels on both singlet [R4(NO+HS(O)O) and R5(H+SO_2+NO)] and triplet [R9(HS(O) O+NO) and R10(H+SO_2+NO)] on the triplet PESs.Among these channels,Channel R2(cis-HONO+~1SO) on the singlet PESs is the favorable channel.The rate constants of above reaction channels were evaluated using classical transition state theory(TST) and Wigner correction.The calculated results showed that the reaction channel of cis-HONO+SO formations is favorable and its rate constant,at 298 K,is 7.78×10-13 cm3·molecule-1·s-1,which is in good agreement with experimental value(9.6×10-12 cm3·molecule-1·s-1).Water molecule catalyzed R2(cis-HONO+~1SO) occurs through two different channels of NO_2+H_2O…HSO and NO_2+H_2O…HSO(HSO+NO_2…H_2O),where the barriers of the two channels respectively are enhanced by 49.97 kcal·mol-1 and 20.67 kcal·mol-1 than that of the naked reaction of R2,indicating that the effect of water molecules on the NO_2+HSO reaction can be neglected in the actual atmospheric environment.
The mechanism for the reaction between NO_2 and HSO was investigated at the CCSD(T)/aug-ccp VTZ//B3 LYP/aug-cc-pVTZ level on both the singlet and triplet potential energy surfaces(PESs).The results showed that there are three hydrogen abstraction reaction channels on both singlet [R1 HN(O) O+~1SO),R2(cisHONO+~1SO),and R3(trans-HONO+~1SO)] and triplet [R6(HN(O) O +~3SO),R7(cis-HONO +~3SO),and R8(trans-HONO+~3SO)] PESs,as well as two oxygen abstraction reaction channels on both singlet [R4(NO+HS(O)O) and R5(H+SO_2+NO)] and triplet [R9(HS(O) O+NO) and R10(H+SO_2+NO)] on the triplet PESs.Among these channels,Channel R2(cis-HONO+~1SO) on the singlet PESs is the favorable channel.The rate constants of above reaction channels were evaluated using classical transition state theory(TST) and Wigner correction.The calculated results showed that the reaction channel of cis-HONO+SO formations is favorable and its rate constant,at 298 K,is 7.78×10-13 cm3·molecule-1·s-1,which is in good agreement with experimental value(9.6×10-12 cm3·molecule-1·s-1).Water molecule catalyzed R2(cis-HONO+~1SO) occurs through two different channels of NO_2+H_2O…HSO and NO_2+H_2O…HSO(HSO+NO_2…H_2O),where the barriers of the two channels respectively are enhanced by 49.97 kcal·mol-1 and 20.67 kcal·mol-1 than that of the naked reaction of R2,indicating that the effect of water molecules on the NO_2+HSO reaction can be neglected in the actual atmospheric environment.
引文
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[3]R Atkinson,D L Baulch,R A Cox et al.J.Phys.Chem.Ref.Data,1992,21(6):1125~1568.
[4]W B De More,S P Sander,D M Golden et al.Jet Propuls.Lab.Publ.,1997,97(4):1~266.
[5]R Atkinson,D L Baulch,R A Cox,et al.IUPACSubcommittee on gas kinetic data evaluation for Atmospheric Chemistry,2001,20.
[6]S S Brown,A R Ravishankara,H Stark.J.Phys.Chem.A,2000,104(30):7044~7052.
[7]N S Wang,C J Howard.J.Phys.Chem.,1990,94(25):8787~8794.
[8]李步通,魏子章,潘清江等.高等学校化学学报,2007,28(6):1107~1109.
[9]L F Chen,D Han,J H Tao et al.J.Remote Sens.,2009,13(3):343~354.
[10]B Langmann,A Heil.Atmos.Chem.Phys.,2004,4(8):2145~2160.
[11]G S Tyndall,A R Ravishankara.Int.J.Chem.Kinet.,2010,23(6):483~527.
[12]R Atkinson,D L Baulch,R A Cox et al.J.Phys.Chem.Ref.Data,1989,21(2):115~150.
[13]R Atkinson,D L Baulch,R A Cox et al.J.Phys.Chem.Ref.Data,1997,26(6):1329~1499.
[14]K V Gothelf,K A Jrgensen.Chem.Rev.,1998,98(2):863~909.
[15]O Tishchenko,S Ilieva,D G Truhlar.J.Chem.Phys.,2010,133(2):021102.
[16]J Z Gillies,C W Gillies,F J Lovas et al.J.Am.Chem.Soc.,1989,113(17):6408~6415.
[17]B Qi,X H Lu,S Y Fang et al.J.Mol.Catal.A,2011,334(1-2):44~51.
[18]M J Frisch,G W Trucks,J A Pople et al.Gaussian 09,revision A.01[CP];Gaussian Inc.:Pittsburgh,PA,2009.
[19]R A B Bond,B S Martincigh,J R Mika et al.J.Chem.Educat.,1998,75(9):1158~1165.
[20]R Gutbrod,E Kraka,R N Schindler et al.J.Am.Chem.Soc.,1997,119(31):7330~7342.
[21]J M Anglada,V M Domingo.J.Phys.Chem.A,2005,109(47):10786~10794.