A theoretical kinetic and classical dynamic investigation of CN+OH and CN+OD reactions on an interpolated potential energy surface

Document Type : Article


Department of Chemistry, Yasouj University, 7493475918 Yasouj, Iran


In the current work, kinetic and dynamic parameters in reactive and non-reactive collisions between CN and OH radicals were investigated upon an interpolated potential energy surface using MP2/6-311G++(d,p) ab-initio method. The total and individual reaction probability and cross-section, for all reactions, were obtained and applied to calculate the rate constant and rate expression. In non-reactive trajectories, the effect of the impact parameter and relative translational energy of particles on the deflection angle was also investigated. To investigate the kinetic isotopic effect, the deuterium was used instead of hydrogen atom to illustrate the effect of mass of attacking radical and target molecule on physical observable such as reaction probability and cross-section


1. Sexton, K. and Adgate, J.L. "Looking at environmental justice from an environmental health perspective", Journal of Exposure Science & Environmental Epidemiology, 9(1), pp. 3-8 (1999).
2. Association, A.L. "Urban air pollution and health inequities: A workshop report", Environmental Health Perspectives, 109(suppl 3), pp. 357-374 (2001).
3. Herbst, E. "Chemistry in the interstellar medium", Annual Review of Physical Chemistry, 46(1), pp. 27- 54 (1995).
4. Hall, P. and Williams, D.A. "Polyatomic molecules in diffuse clouds", Astrophysics and Space Science, 229(1), pp. 49-61 (1995).
5. Oran, E.S. "Astrophysical combustion", Proceedings of the Combustion Institute, 30(2), pp. 1823-1840 (2005).
6. Sharafdini, R. and Ramazani, S. "Dynamic and kinetic parameters and energy exchanges of particles in reaction of NH+OH and deuterated analogues on an interpolated potential energy surface", Chemistry Select., 5(12), pp. 3518-3528 (2020).
7. Lique, F., Dubernet, M.l., Spielfiedel, A., et al. "Rotational excitation of sulfur monoxide in collision with helium at high temperature", Astronomy & Astrophysics, 450(1), pp. 399-405 (2006).
8. Tobo la, R., Dumouchel, F., Klos, J., et al. "Calculations of fine-structure resolved collisional rate coefficients for the NH(X3)-He system", The Journal of Chemical Physics, 134(2), pp. 024305-024313 (2011).
9. Warnatz, J., Maas, U., and Dibble, R.W., Physical and Chemical Fundamentals, Modeling and Simulation, Experiments, Pollutant Formation, Springer, Berlin, Frenklach, M, Wang, H (1990).
10. WC Jr, G., Gas-Phase Combustion Chemistry, Springer Science & Business Media (1999).
11. Miller, J.A. and Bowman, C. "Mechanism and modeling of nitrogen chemistry in combustion", Prog. Energy Combust. Sci., 15, pp. 287-338 (1989).
12. Cherchneff, I. and Glassgold, A.E. "The formation of carbon chain molecules in IRC+10216", The Astrophysical Journal, 419, pp. 41-44 (1993).
13. Millar, T. and Herbst, E. "A new chemical model of the circumstellar envelope surrounding IRC+ 10216", Astronomy and Astrophysics, 288, pp. 561-571 (1994).
14. Doty, S.D. and Leung, C.M. "Detailed chemical modeling of the circumstellar envelopes of carbon stars: Application to IRC+10216", The Astrophysical Journal, 502(2), pp. 898-908 (1998).
15. Wooldridge, S.T., Hanson, R.K., and Bowman, C.T. "A shock tube study of reactions of CN with HCN, OH, and H2 using CN and OH laser absorption", International Journal of Chemical Kinetics, 28(4), pp. 245-258 (1996).
16. A0Hearn, M.F., Hoban, S., Birch, V., et al. "Cyanogen jets in comet Halley", Nature, 324, pp. 649-651 (1986).
17. Liu, K. and Wagner, A.F., The Chemical Dynamics and Kinetics of Small Radicals, World Scientific, Singapore (1995).
18. Ruscic, B., Feller, D., Dixon, D.A., et al. "Evidence for a lower enthalpy of formation of hydroxyl radical and a lower gas-phase bond dissociation energy of water", The Journal of Physical Chemistry A, 105(1), pp. 1-4 (2001).
19. Lee, T.J. and Rendell, A.P. "The structure and energetics of the HCN-HNC transition state", Chemical Physics Letters, 177(6), pp. 491-497 (1991).
20. Rinnenthal, J.L. and Gericke, K.H. "Direct highresolution determination of the singlet-triplet splitting in NH using stimulated emission pumping", Journal of Molecular Spectroscopy, 198(1), pp. 115-122 (1999).
21. Zyrianov, M., Droz-Georget, Th., Sanov, A., et al. "Competitive photodissociation channels in jet-cooled HNCO: Thermochemistry and near-threshold predissociation", The Journal of Chemical Physics, 105(18), pp. 8111-8116 (1996).
22. Decker, B.K. and Macdonald, R.G. "Determination of the rate constant for the tadical-radical reaction CN(X2+)+OH(X2) at 292 K", The Journal of Physical Chemistry A, 107(43), pp. 9137-9146 (2003).
23. Frisch, M., Trucks, G.W., Schlegel, H.B., et al., Gaussian 03, Revision c. 02; Gaussian, Inc., Wallingford, CT, 4 (2004).
24. Collins, M.A. "Molecular potential-energy surfaces for chemical reaction dynamics", Theoretical Chemistry Accounts, 108(6), pp. 313-324 (2002).
25. Ischtwan, J. and Collins, M.A. "Molecular potential energy surfaces by interpolation", The Journal of Chemical Physics, 100(11), pp. 8080-8088 (1994).
26. Thompson, K.C., Jordan, M.J., and Collins, M.A. "Polyatomic molecular potential energy surfaces by interpolation in local internal coordinates", The Journal of Chemical Physics, 108(20), pp. 8302-8316 (1998).
27. Ramazani, S., Frankcombe, T.J., Andersson, S., et al. "The dynamics of the H2+CO+ reaction on an interpolated potential energy surface", J. Chem. Phys., 130(24), pp. 244302-244311 (2009).
28. Bettens, R.P. and Collins, M.A. "Learning to interpolate molecular potential energy surfaces with confidence: A Bayesian approach", The Journal of Chemical Physics, 111(3), pp. 816-826 (1999).
29. Jordan, M.J., Thompson, K.C., and Collins, M.A. "The utility of higher order derivatives in constructing molecular potential energy surfaces by interpolation", The Journal of Chemical Physics, 103(22), pp. 9669- 9675 (1995).
30. Farwig, R. "Multivariate interpolation of scattered data by moving least squares methods", in Algorithms for Approximation, Clarendon Press, pp. 193-211 (1987).
31. Lancaster, P. and Salkauskas, K., Curve and Surface Fitting, An Introduction, London, Academic Press (1986).
32. Sharafdini, R. and Ramazani, S. "Molecular potential energy surface constructed from ab initio interpolation for HCN+H reaction and deuterated analogues", Molecular Physics, 115(7), pp. 860-868 (2017).
33. Padash, R. and Ramazani, S. "Collision processes, dynamic and kinetic parameters, and energy exchanges of particles in astrochemistry reaction of NH +H2 and deuterated analogs on an interpolated potential energy surface", Molecular Astrophysics, 20(3), pp. 1- 49 (2020).
34. Dashtaki, S.L.H. and Ramazani, S. "Variational transition state theory with multidimensional tunnelling and kinetic isotope effects in the reactions of C2H6, C2H5D and C2D6 with CCl3 to produce CHCl3 and CDCl3", Molecular Physics, 114(14), pp. 2195-2203 (2016).
35. Ramazani, S. "Direct-dynamics VTST study of hydrogen or deuterium abstraction and C|C bond formation or dissociation in the reactions of CH3+CH4, CH3+CD4, CH3D+CD3, CH3CH3+H, and CH3CD3+D", The Journal of Chemical Physics, 138(19), pp. 194305-194315 (2013).
36. Kunc, J.A. "Analytical dependence of the viscosity cross sections and viscosity coefficients on parameters of intermolecular potentials", The Journal of Chemical Physics, 99(6), pp. 4705-4717 (1993).
37. Zhang, L., Liu, D., Song, Y., et al. "Examining the isotope effect on CH decay and H exchange reactions: H(2S)+CH(D/T) (2)", Physica Scripta, 96(1), pp. 015404-015410 (2020).