Abstract
A theoretical study on the mechanism of the reactions of methyl difluoroacetate (MDFA) CF2HC(O)OCH3 with Cl atoms is presented. Two conformers relatively close in energy have been identified for MDFA. Geometry optimization and frequency calculations have been performed at the MPWB1K/6-31+G(d,p) level of theory, and energetic information is further refined by calculating the energy of the species using G2(MP2) theory. Transition states (TSs) are searched on the potential energy surface involved during the reaction channels, and each of the TSs is characterized by the presence of only one imaginary frequency. The existence of TSs on the corresponding potential energy surface is ascertained by performing intrinsic reaction coordinate calculation. Our calculations reveal that hydrogen abstraction from the –CH3 group is thermodynamically and kinetically more facile than that from the –CF2H group. Theoretically calculated rate constants at 298 K using the canonical transition state theory are found to be in good agreement with the experimentally measured ones. The atmospheric lifetime of CF2HC(O)OCH3 was estimated to be 16 years. The atmospheric fate and the main degradation process of alkoxy radical CF2HC(O)OCH2O are also discussed for the first time. Our calculation indicates that the fluorine atoms substitution has deactivating effect for the α-ester rearrangement.
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Farman JD, Gardiner BG, Shanklin JD (1985) Nature 315:207–210
Sekiya A, Misaki S (2000) J Fluor Chem 101:215–221
Ravishankara RA, Turnipseed AA, Jensen NR, Barone S, Mills M, Howark CJ, Solomon S (1994) Science 263:71–75
Urata S, Takada A, Uchimaru T, Chandra AK (2003) Chem Phys Lett 368:215–223
Singh HJ, Mishra BK (2010) J Mol Model 16:1473–1480
Wallington TJ, Schneider WF, Sehested J, Bilde M, Platz J, Nielsen OJ, Christensen LK, Molina MJ, Molina LT, Wooldridge PW (1997) J Phys Chem A 101:8264–8274
Ninomiya Y, Kawasaki M, Guschin A, Molina LT, Molina MJ, Wallington TJ (2000) Environ Sci Technol 34(14):2973–2978
Chen L, Kutsuna S, Tokuhashi K, Sekiya A, Tamai R, Hibino Y (2005) J Phys Chem A 109:4766–4771
Singh HJ, Mishra BK (2011) J Mol Model 17:415–422
Urata S, Takada A, Uchimaru T, Chandra AK (2003) Chem Phys Lett 368:215–223
Singh HJ, Mishra BK, Rao PK (2010) Bull Korean Chem Soc 31:3718–3722
Nohara K, Toma M, Kutsuna S, Takeuchi K, Ibusuki T (2001) Environ Sci Technol 35(1):114–120
Bravo I, Dıaz-de-Mera Y, Aranda A, Moreno E, Nutt DR, Marston G (2011) Phys Chem Chem Phys 13:17185–17193
Dalmasso PR, Taccone RA, Nieto JD, Teruel MA, Lane SI (2006) Atmos Environ 40:7298–7303
Wingenter OW, Kubo MK, Blake NJ, Smith TW, Blake DR (1996) J Geophys Res 101:4331–4340
Sulback AMP, Nielsen OJ, Wallington TJ, Hurley MD, DeMoore GW (2005) J Phys Chem A 109:3926–3934
Jordan A, Frank H (1999) Environ Sci Technol 33(4):522–527
Tanaka T, Doi T, Okada S, Yamaki J (2009) Fuel Cells 09:269–272
Zhao L, Okada S, Yamaki J (2013) J Power Sources 244:369–374
Olivier B, Karol L WO, Patent 2,007,093,567
Zheng S-Z, Cao X-Y, Zhou Q, Wang S-H, Hua G-S, Lu J-Q, Luo M-F, Wang Y-J (2013) J Fluor Chem 145:132–135
Blanco MB, Teruel MA (2007) Atmos Environ 41(34):7330–7338
Blanco MB, Bejan I, Barnes I, Wiesen P, Teruel MA (2008) Chem Phys Lett 453:18–23
Singh HJ, Tiwari L, Rao PK, Mol Phys. doi:10.1080/00268976.2013.868554
Blanco MB, Bejan I, Barnes I, Wiesen P, Teruel MA (2010) Environ Sci Technol 44:2354–2359
Henon E, Bohr F, Gomex NS, Caralp F (2003) Phys Chem Chem Phys 5:5431–5437
Ferenac MA, Davis AJ, Holloway AS, Dibble TS (2003) J Phys Chem A 107:63–72
Singh HJ, Mishra BK, Gour NK (2010) Theor Chem Acc 125:57–64
Vereecken L, Peeters J (2009) Phys Chem Chem Phys 11:9062–9074
Singh HJ, Mishra BK, Rao PK (2012) Can J Chem 90:403–409
Singh HJ, Mishra BK (2011) J Chem Sci 123:733–741
Zhao Y, Truhlar DG (2004) J Phys Chem A 108:6908–6918
Zeegers-Huyskens T, Lily M, Sutradhar D, Chandra AK (2013) J Phys Chem A 117:8010–8016
Chakrabatty AK, Mishra BK, Bhattacharjee D, Deka RC (2013) J Fluor Chem 154:60–66
Hratchian HP, Schlegel HB (2005) J Chem Theory Comput 1:61–69
Curtiss LA, Raghavachari K, Pople JA (1993) J Chem Phys 98:1293–1298
Chakrabatty AK, Mishra BK, Bhattacharjee D, Deka RC (2013) Mol Phys 111:860–867
Chandra AK (2012) J Mol Model 18:4239–4247
Mishra BK, Chakrabatty AK, Deka RC (2013) J Mol Model 19:3263–3270
Devi KhJ, Chandra AK (2011) Comput Theor Chem 965:268–274
Mishra BK, Chakrabatty AK, Deka RC (2014) Struct Chem 25:463–470
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V,Mennucci B, Petersson GA, Nakatsuji H, CaricatoM, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, EharaM, ToyotaK, FukudaR, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA Jr., Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell K, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2010) Gaussian 09, revision B.01. Gaussian Inc., Wallingford
Abraham RJ, Tormenab CF, Rittner R (2001) J Chem Soc Perkin Trans 2:815–820
Laidler KJ (2004) Chemical Kinetics, 3rd edn. Pearson Education, New Delhi
Johnston HS, Heicklen J (1962) J Phys Chem 66:532–533
Truhlar DG, Chuang YY (2000) J Chem Phys 112:1221–1228
Truhlar DG (1991) J Comput Chem 12:266–270
Papadimitriou VC, Kambanis KG, Lazarou YG, Papagiannakopoulos P (2004) J Phys Chem A 108:2666–2674
Spicer CW, Chapman EG, Finlayson-Pitts BJ, Plastridge RA, Hubbe JM, Fast JD, Berkowitz CM (1998) Nature 394:353–356
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The authors acknowledge the financial support from the Department of Science and Technology, New Delhi in the form of a project (SR/NM.NS-1023/2011(G)). BKM is thankful to University Grants Commission, New Delhi for providing Dr. D. S. Kothari Fellowship.
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Deka, R.C., Mishra, B.K. Theoretical investigation of the atmospheric chemistry of methyl difluoroacetate: reaction with Cl atoms and fate of alkoxy radical at 298 K. Struct Chem 25, 1475–1482 (2014). https://doi.org/10.1007/s11224-014-0425-3
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DOI: https://doi.org/10.1007/s11224-014-0425-3