Ab initio study of the mechanism of the reaction ClO + O --> Cl + O2

  • S. Naskar Diamond Harbour Women’s University
  • G. Nandi Diamond Harbour Women’s University
  • T. K. Ghosh Diamond Harbour Women's University
Keywords: Electronic structure, reaction mechanism, ozone depleting reaction

Abstract

Abstract. Ab initio investigation on the reaction mechanism of ClO + O --> Cl + O2 reaction has been performed using correlation consistent triple zeta basis set. The geometry and frequency of the reactants, products, minimum energy geometries and transition states are obtained using MP2 method and energetics are obtained at the QCISD(T)//MP2 level of theory. Primarily, a possible reaction mechanism is obtained on the basis on IRC calculations using MP2 level of theory. To obtain true picture of the reaction path, we performed IRC calculations using CASSCF method with a minimal basis set 6-31G**. Some new equilibrium geometries and transition states have been identified at the CASSCF level. Energetics are also obtained at the QCISD(T)//CASSCF method. Possible reaction paths have been discussed, which are new in literature. Heat of reaction is found to be consistent with the experimental data. Bond dissociation energies to various dissociation paths are also reported.

Author Biographies

S. Naskar, Diamond Harbour Women’s University

Department of Physics

G. Nandi, Diamond Harbour Women’s University

Department of Physics.

T. K. Ghosh, Diamond Harbour Women's University

Department of Physics.

References

Molina, M. J.; Rowland, F. S. Nature. 1974, 249, 810-812. DOI: https://doi.org/10.1038/249810a0

Stolarski, R. S.; Cicerone, R. J. Can J. Chem. 1974, 52, 1610-1615. DOI: https://dx.doi.org/10.1139/v74-233

Schwab, J. J.; Toohey, D. W.; Brune, W. H.; Anderson, J. G. J. Geophys. Res. 1984, 89, 9581-9587. DOI: https://dx.doi.org/10.1029/JD089iD06p09581

Ongstad, A. P.; Birks, J. W. J. Chem. Phys. 1986, 85, 3359-3368. DOI: https://dx.doi.org/10.1063/1.450957

Goldfarb, L.; Burkholder, J. B.; Ravishankara, A. R. J. Phys. Chem. A. 2001, 105, 5402-5409. DOI: https://dx.doi.org/10.1021/jp0100351

Arkell, A.; Schwager, I. J. Am. Chem. Soc. 1967, 89, 5999-6006. DOI: https://dx.doi.org/10.1021/ja01000a001

Gole, J. L. J. Phys. Chem. 1980, 84, 1333-1340. DOI: https://dx.doi.org/10.1021/j100448a009

Johnsson, K.; Engdahl, A.; and Nelander, B. J. Phys. Chem. 1993, 97, 9603-9606. DOI: https://dx.doi.org/10.1021/j100140a013

Miyazaki, K.; Tanoura, M.; Tanaka, K.,; Tanaka, T. J. Mol. Spectrosc. 1986, 116, 435-449. DOI: https://dx.doi.org/10.1016/0022-2852(86)90138-4

Muller, H. S. P.; Willner, H. J. Phys. Chem. 1993, 97, 10589-10598. DOI: https://dx.doi.org/10.1021/j100143a013.

Francisco, J. S.; Sander, S. P. J. Chem. Phys. 1993, 99, 2897-2901. DOI: https://dx.doi.org/10.1063/1.465197

Beltrán, A.; Andrés, J.; Noury, S.; Silvi, B. J. Phys. Chem. A. 1999, 103, 3078-3088. DOI: https://dx.doi.org/10.1021/jp983999

Li, Q. -S.; Lu, S.-F.; Xu, W.-G.; Xie, Y.; Schaefer III, H. F. J. Phys. Chem. A 2002, 106, 12324-12330. DOI: https://dx.doi.org/10.1021/jp020362o

Peterson, K. A.; Werner, H. J. J. Chem. Phys. 1992, 96, 8948-8961. DOI: https://dx.doi.org/10.1063/1.462253

Zhu.; R. S.; Lin, M. C. J. Chem. Phys. 2003, 119, 2075-2082. DOI: https://dx.doi.org/10.1063/1.1585027

Basis set exchange for quantum chemistry: https://www.basissetexchange.org

Chase, M. W. J. Phys. Chem. Ref. Data, Monograph No.9, NIST-JANAF Thermochemical Tables, 4th ed. 1998.

C. E. Moore, Atomic Energy Levels, NSRDS-NBS 35, Vol. 1, 3, Washington, DC, 1971.

Frisch, M. J.; et al., Gaussian 03W, Gaussian, Inc., Wallingbond, CT, 2003.

Huber, K. P.; Herzberg, G. Molecular Spectra and Molecular Structure: Constants of Diatomic Molecules, Vol. IV, Van Nostrand, New York, 1979.

Peterson, K. A.; Shepler, B. C.; Figgen, D.; Stoll, H. J. Phys. Chem. A. 2006, 110, 13877-13883. DOI: https://dx.doi.org/10.1021/jp065887l

Hassanzadeh, P.; Irikura, K. K.; Johnson III, R. D. J. Phys. Chem. A. 1997, 101, 6897-6902. DOI: https://dx.doi.org/10.1021/jp971007e

Grant, D. J.; Garner III, E. B.; Matus, M. H.; Nguyen, M. T.; Peterson, K. A.; Francisco, J. S.; Dixon, D. A. J. Phys. Chem. A 2010, 114, 4254–4265. DOI: https://dx.doi.org/10.1021/jp911320p

Published
12-27-2021
Section
Regular Articles