caa a22 4500 605512531 CHVBK 20210128100656.0 cr unu---uuuuu 210128e20150401xx s 000 0 eng 10.1007/s00894-015-2629-x doi (NATIONALLICENCE)springer-10.1007/s00894-015-2629-x Theoretical insight on atmospheric chemistry of HFE-365mcf3: reactions with OH radicals, atmospheric lifetime, and fate of alkoxy radicals (CF3CF2CH(O•)OCH3/CF3CF2CH2OCH2O•) [Elektronische Daten] [Debajyoti Bhattacharjee, Bhupesh Mishra, Ramesh Deka] In the present work, theoretical study on the mechanism and kinetics of the gas-phase reactions of CF3CF2CH2OCH3 (HFE-365mcf3) with the OH radicals have been performed using meta-hybrid modern density functional M06-2X in conjunction with 6-31+G(d,p) basis set. Reaction profiles for OH-initiated hydrogen abstraction are modeled including the formation of pre-reactive and post-reactive complexes at entrance and exit channels. Our calculations reveal that hydrogen abstraction from the -CH2 group is thermodynamically more facile than that from the -CH3 group. This is further ascertained by the calculated C-H bond dissociation energy of CF3CF2CH2OCH3 molecule. The rate constants of the titled reactions are computed over the temperature range of 250-450K. The calculated rate constant value at 298K is found to be in reasonable agreement with the experimental results. The atmospheric life time of HFE-365mcf3 is estimated to be 42days. The atmospheric fate of the alkoxy radicals, CF3CF2CH(O•)OCH3 and CF3CF2CH2OCH2O• are also investigated for the first time using the same level of theory. Out of three plausible decomposition channels, our results clearly point out that reaction with O2 is the dominant atmospheric sink for the decomposition of CF3CF2CH(O•)OCH3 radical in the atmosphere. Springer-Verlag Berlin Heidelberg, 2015 Alkoxy radical nationallicence Bond dissociation energy nationallicence Hydrofluoroether nationallicence Isodesmic reactions nationallicence Rate constant nationallicence Bhattacharjee Debajyoti Department of Chemical Sciences, Tezpur University, Napaam, 784028, Tezpur, Assam, India aut Mishra Bhupesh Department of Chemistry, D. N. Government College, 791113, Itanagar, Arunachal Pradesh, India aut Deka Ramesh Department of Chemical Sciences, Tezpur University, Napaam, 784028, Tezpur, Assam, India aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-8 1610-2940 21:4<1 2015 21 894 https://doi.org/10.1007/s00894-015-2629-x text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2629-x text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Bhattacharjee Debajyoti Department of Chemical Sciences, Tezpur University, Napaam, 784028, Tezpur, Assam, India aut NATIONALLICENCE 700 1- Mishra Bhupesh Department of Chemistry, D. N. Government College, 791113, Itanagar, Arunachal Pradesh, India aut NATIONALLICENCE 700 1- Deka Ramesh Department of Chemical Sciences, Tezpur University, Napaam, 784028, Tezpur, Assam, India aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-8 1610-2940 21:4<1 2015 21 894