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Theoretical Chemistry Accounts

, Volume 127, Issue 5–6, pp 551–560 | Cite as

Theoretical studies of the reactions of Cl atoms with CF3CH2OCH n F(3−n) (n = 1, 2, 3)

  • Hui ZhangEmail author
  • Cheng-yang Liu
  • Gui-ling Zhang
  • Wen-jie Hou
  • Miao Sun
  • Bo Liu
  • Ze-sheng LiEmail author
Regular Article

Abstract

This paper presents the theoretical studies of the reactions of Cl atoms with CF3CH2OCH3, CF3CH2OCH2F and CF3CH2OCHF2 using an ab initio direct dynamics theory. The geometries and vibrational frequencies of the reactants, complexes, transition states and products are calculated at the MP2/6-31+(d,p) level. The minimum energy path is also calculated at same level. The MC-QCISD method is carried out for further refining the energetic information. The rate constants are evaluated with the canonical variational transition state theory (CVT) and CVT with small curvature tunneling contributions in the temperature range 200–1,500 K. The results are in good agreement with experimental values.

Keywords

Ab initio HFEs CVT Rate constants 

Notes

Acknowledgments

The authors thank Professor Donald G. Truhlar for providing POLYRATE 9.1 program. This work is supported by the National Natural Science Foundation of China (50743013, 20973049), the Foundation for University Key Teacher by the Department of Education of Heilongjiang Province (1152G010), the SF for leading experts in academe of Harbin of China (2007RFXXG027), the SF for Postdoctoral of Heilongjiang province of China (LBH-Q07058), and Natural Science Foundation of Heilongjiang Province (B200605), The Foundation of Graduate Innovation of the Education Department of Heilongjiang province (YJSCX2009-055HLJ).

Supplementary material

214_2010_746_MOESM1_ESM.docx (1.3 mb)
Supporting Information Available: Table S1 Calculated frequencies (cm−1) for the transitions states at the MP2/6-31+G(d,p) level. Table S2 Calculated and experimental frequencies (cm−1) for the reactants, products and complexes at the MP2/6-31+G(d,p) level. Table S3 Relative energies of the stationary points in terms of enthalpy and Gibbs free energy (Hartree) calculated at the MP2/6-31+G(d,p) level. Table S4 The TST, CVT, ZCT and SCT rate constants calculated at the MC-QCISD//MP2/6-31+G(d,p) level for three reactions, R1, R2, and R3, between 200 and 1,500 K (cmmolecule−1 s−1). Fig. S1 Optimized geometries of the reactants, complexes and products at the MP2/6-31+G(d,p) level. (DOCX 1359 kb)

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Copyright information

© Springer-Verlag 2010

Authors and Affiliations

  1. 1.College of Chemical and Environmental EngineeringHarbin University of Science and TechnologyHarbinPeople’s Republic of China
  2. 2.Academy of Fundamental and Interdisciplinary Sciences, Department of ChemistryHarbin Institute of TechnologyHarbinPeople’s Republic of China
  3. 3.School of Sciences, Beijing Institute of TechnologyBeijingPeople’s Republic of China

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