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Investigation of Transition state and Kinetics of the reaction of NCO+O

Investigation of Transition state and Kinetics of the reaction of NCO+O. By Ruchira Silva. Over view. Back ground Experimental Results Recent theoretical results Selected project and calculation Results Conclusion. Why NCO + O ?. NO x emission effects - air quality

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Investigation of Transition state and Kinetics of the reaction of NCO+O

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  1. Investigation of Transition state and Kinetics of the reaction of NCO+O By Ruchira Silva

  2. Over view • Back ground • Experimental Results • Recent theoretical results • Selected project and calculation • Results • Conclusion

  3. Why NCO + O ? • NOx emission effects - air quality • Three sources of NOx formation • NCO – key in two mechanism

  4. Three reaction paths • NCO (X2Π) + O(3P) NO (X2Π) + CO (X1∑) • NCO (X2Π) + O(3P) N (4S) + CO2 (X1∑) • NCO (X2Π) + O(3P) N (2D) +CO2 (X1∑)

  5. Experimental studies • Yide Gao and R. glen Macdonald • Determination of rate constant using time resolved IR absorption spectroscopy. • Rate constant = (2.1 ± 0.76) x 10-10cm3molecule-1s-1) at 292 ± 2 K • K.H. Becker, R.Kurtenbach, F.Schmidt and P.waesen • Determination of rate constant using laser induced florescence • Rate constant = Combustion and flame 120:570-577 (2000) : J.Phys.Chem.A 2003, 107, 4625-4635

  6. Theoretical studies • Zheng-wang Qu, Hui Zhu, Ze-sheng Li, Xing-kang Zhang and Qi- yuan Zhang • Reaction mechanism between CN and O2 • Reaction followed through NCO (X2Π) + O(3P) or • NO (X2Π) + CO (X1∑) channel Z.Qu et al Chemical Physics Letters 353 (2002) 304-309

  7. Level of theory and Basis set • Geometry optimization • Theory – UB3LYP • Basis set – 6-31+G(d) • Zero point energy • Calculated frequency + statistical method • Relative energy • Theory – UCCSD(T) • Basis set – 6-311+G(d)

  8. Z.Qu et al Chemical Physics Letters 353 (2002) 304-309

  9. Z.Qu et al Chemical Physics Letters 353 (2002) 304-309

  10. TS 3/6 Z.Qu et al Chemical Physics Letters 353 (2002) 304-309

  11. ? Z.Qu et al Chemical Physics Letters 353 (2002) 304-309

  12. Geometry Optimization • Initially • Theory and Basis set - UHF/3-21+G* • Finally • Theory and Basis set – UB3LYP/6-31+G(d) • Theory and Basis set – compound (G2) Energy calculation

  13. Results Structure -3

  14. Results Structure -6

  15. Results Transition Structure - 6~3

  16. Energy Calculation

  17. Results Results • Relative energies • Relative energies (kcal/mol) – UHF/3-21+G* ? TS 6-3 65.98078 Structure 6 0.00000 Structure 3

  18. Results • Relative energies (kcal/mol) – UB3LYP/6-31+G(d) ? TS 6-3 34.81763 Structure 6 0.00000 Structure 3

  19. Future plan • Find the Transition state between structure (6) and (3) • Find kinetics the intermediate reaction • Find kinetics of full reaction • Find a new mechanism to the reaction

  20. Summery • NCO (X2Π) + O(3P) NO (X2Π) + CO (X1∑) involves multiple steps • Reaction path from 6 to 3 go through a transition state • Electronic structure of the TS is not common

  21. Acknowledgment • Professor. ArthurG. Suits • Professor. H. Bernhard Schlegel • Dr. Smriti Anand • Dr. Hrant P. Hratchian • Wayne State University • My friends.

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