Abstract
During the past decade, many new results have been obtained on the dynamics of elementary chemical reactions. One of the most intensively studied reactions continues to be the process F + H2(v,j) → FH(v′,j′) + H. Many experimental and theoretical results on this reaction have been discussed in recent reviews.1,2 On the experimental side, the F + H2 reaction with isotopic variants has been studied under chemical laser conditions,3-5 through IR chemiluminescence,6,7 and in crossed molecular beam machines.8,9 Recent crossed beam studies by Sparks et al. 9 are particularly relevant to the present study and will be discussed in more detail later in this section. On the theoretical side, very extensive quasiclassical trajectory studies on a number of potential surfaces have provided many new dynamical results for the three-dimensional reactions.1,2,10 The first quantum collinear studies11-13 of this reaction showed a dramatic difference from the low-energy quasiclassical results12 for the collinear reaction. At these low energies, there is a sharp resonance in the quantum mechanical v=0→v′=2 reaction probability curve, followed by a slow growth In the 0 → 3 reaction probability. The 0 → 2 resonance is the most striking feature of the low-energy collinear reaction. Since these first quantum collinear studies, many other quantum studies of the collinear reaction have appeared.14-16 Connor has recently presented a comprehensive review of these results.16 In attempting to understand the origin of the 0 → 2 collinear resonnance, Latham et al. 15 displayed plots of the scattering wavefunction and flux in the interaction region. In addition, Hayes and Walker17 have recently found that removal of the 0.05 eV entrance-channel barrier destroys this sharp resonance feature.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
J. B. Anderson, The reaction F + H2 → HF + H, Advan. Chem. Phys. 41: 229 (1980).
J. T. Muckerman, Applications of classical trajectory techniques to reactive scattering, Theor. Chem.: Advan. Perspectives 6A: 1 (1981).
J. H. Parker and G. C. Pimentel, Vibrational energy distribution through chemical laser studies I. Fluorine atoms plus hydrogen or methane, J. Chem. Phys. 51: 91 (1969).
R. D. Coombe and G. C. Pimentel, Effects of rotation on the vibrational energy distributions in the reaction F + H2, J. Chem. Phys. 59: 251 (1973).
M. Berry, F + H2, D2, HD reactions: Chemical laser determination of the product vibrational state populations and the F + HD intramolecular kinetic isotope effect, J. Chem. Phys. 59: 6229 (1973).
J. C. Polanyi and K, B. Woodall, Energy distribution among reaction products. VI. F + H2, D2, J. Chem. Phys. 57: 1574 (1972).
D. S. Perry and J. C. Polanyi, Energy distribution among reaction products. IX. F + H2, HD, D2, J. Chem. Phys, 12: 419 (1976).
T. P. Schafer, P. E. Siska, J. M. Parson, F. P. Tully, Y. C. Wong, and Y. T. Lee, Cross molecular beam study of F + D2, J. Chem. Phys. 53: 3385 (1970).
R. K. Sparks, C. C. Hayden, K. Shobatake, D. M. Neumark, and Y. T. Lee, Molecular beam studies of reaction dynamics of F + H2, D2, in: “Horizons of Quantum Chemistry”, K. Fukui and B. Pullman, eds., Reidel, Dordrecht (1980), p. 91.
J. C. Polanyi and J. L. Schreiber, The reaction F + H2 → FH + H. A case study in reaction dynamics, Faraday Disc. Chem. Soc. 62: 267 (1977).
S. F. Wu, B. R. Johnson, and R. D. Levine, Quantum mechanical computational studies of chemical reactions: III. Collinear A + BC reaction with some model potential energy surfaces, Mol. Phys. 25: 839 (1973).
G. C. Schatz, J. M. Bowman, and A. Kuppermann, Exact quantum, quasiclassical, and semiclassical reaction probabilities for the collinear F + H2 → FH + H reaction, J. Chem. Phys. 63: 674 (1975).
J. N. L. Connor, W. Jakubetz, and J. Manz, Exact quantum transition probabilities by the state path sum method: Collinear F + H2 reaction, Mol. Phys. 29: 347 (1975).
C. Zuhrt, T. Kamal, and L. Zülicke, Quantum mechanical investigations of the collinear collisions F + H2 and F + D2 using the wavepacket approach, Chem. Phys. Lett. 36: 396 (1975).
S. L. Latham, J. F. McNutt, R. E. Wyatt, and M. J. Redmon, Quantum dynamics of the F + H2 reaction: Resonance models and energy and flux distributions in the transition state, J. Chem. Phys. 69: 3746 (1978).
J. N. L. Connor, Reactive molecular collision calculations, Comput. Phys. Commun. 17: 117 (1979).
E. F. Hayes and R. B. Walker, private communication.
A. Kafri, Y. Shimoni, R. D. Levine, and S. Alexander, The Born approximation as a simple diagnostic method for direct molecular collisions with applications to the Cl + HI and F + H2 reactions, Chem. Phys. 13: 323 (1976).
Y. Shan, B. H. Choi, R. T. Poe, and K. T. Tang, Three-dimensional quantum mechanical study of the F + H2 reactive scattering, Chem. Phys. Lett. 57: 379 (1978).
M. Baer, V. Khare, and D. Kouri, private communication.
R. E. Wyatt, Quantum mechanics of neutral atom-diatomic molecular reactions, in: “State-to-State Chemistry”, P. R. Brooks and E. F. Hayes, eds., American Chemical Society, Washington (1977), p. 185.
M. J. Redmon and R. E. Wyatt, Three-dimensional quantum mechanical studies of the H + H2 and F + H2 reactions, Int. J. Quantum Chem. Symp. 9: 403 (1975).
M. J. Redmon and R. E. Wyatt, Computational methods for reactive scattering, Int. J. Quantum Chem. Symp. 11: 343 (1977).
M. J. Redmon, Recent results from three-dimensional quantum reactive scattering theory, Int. J. Quantum Chem. Symp. 13: 559 (1979).
M. J. Redmon and R. E. Wyatt, Quantum resonance structure in the three-dimensional F + H2 reaction, Chem. Phys. Lett. 63: 209 (1979).
R. E. Wyatt, Quantum mechanical study of chemical reaction dynamics, in: “Horizons of Quantum Chemistry”, K. Fukui and B. Pullman, eds., Reidel, Dordrecht (1980), p. 63.
R. E. Wyatt, to be published.
R. A. Marcus, Analytical mechanics of chemical reactions. III. Natural collision coordinates, J. Chem. Phys. 49: 2610 (1968).
J. C. Light and R. B. Walker, Hermitian quantum equations for scattering in reaction coordinates, J. Chem. Phys. 65: 1598 (1976).
J. T. Muckerman, Classical dynamics of the reaction of fluorine atoms with hydorgen molecules. II. Dependence on the potential energy surface, J. Chem. Phys. 56: 2997 (1972).
J. C. Light and R. B. Walker, An R-matrix approach to the solution of coupled equations for atom-molecule reactive scattering, J. Chem. Phys. 65: 4272 (1976).
P. B. Middleton and R. E. Wyatt, Quantum mechanical study of a reaction path bifurcation model, Chem. Phys. Lett. 21: 57 (1973).
S. H. Harms, A. B. Elkowitz, and R. E. Wyatt, Asymmetric top states for chemical reactions, Mol. Phys. 31: 177 (1976).
R. E. Wyatt, Direct mode reactions: Methodology for accurate quantal calculations, in “Atom-Molecule Collision Theory: A Guide for the Experimentalist”, R. B. Bernstein, ed., Plenum, New York (1979), p. 567.
J. W. Duff and D. G. Truhlar, Effect of curvature on the reaction path on dynamic effects in endothermic reactions and product energies in exothermic reactions, J. Chem. Phys. 62: 2477 (1975).
D. G. Truhlar and D. A. Dixon, Direct-mode chemical reactions: Classical theories, in “Atom-Molecule Collision Theory: A Guide for the Experimentalist”, R. B. Bernstein, ed., Plenum, New York (1979), p. 595, and references therein.
D. G. Truhlar, B. C. Garrett, and R. S. Grev, unpublished; D. G. Truhlar, personal communication.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1981 Springer Science+Business Media New York
About this chapter
Cite this chapter
McNutt, J.F., Wyatt, R.E. (1981). Quantum Dynamics of the Three-Dimensional F + H2 Reaction: Wavefunction Density Analysis. In: Truhlar, D.G. (eds) Potential Energy Surfaces and Dynamics Calculations. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-1735-8_20
Download citation
DOI: https://doi.org/10.1007/978-1-4757-1735-8_20
Publisher Name: Springer, Boston, MA
Print ISBN: 978-1-4757-1737-2
Online ISBN: 978-1-4757-1735-8
eBook Packages: Springer Book Archive