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Lattice influence on gas–solid desorption: RRKM model
1.For recent reviews of thermal desorption, see for example, L. A. Péterman, in Progress in Surface Science, edited by S. G. Davison (Pergamon, New York, 1972), Vol. 3, Pt. 1, p. 1;
1.V. N. Ageen and N. I. Ionov, ibid., Vol. 5, Pt. 1, p. 1;
1.D. Menzel, in Interactions on Metal Surfaces, edited by R. Cormer (Springer, Berlin, 1975), Chap. 7;
1.and D. A. King, Surf. Sci. 47, 384 (1975).
2.S. A. Adelman and B. J. Garrison, J. Chem. Phys. 65, 3751 (1976).
3.J. D. Doll and D. R. Dion, J. Chem. Phys. 65, 3762 (1976).
4.B. J. Garrison and S. A. Adelman, Surf. Sci. “Generalized Langevin Theory for Gas‐Solid Processes: Inelastic Scattering Studied,” (in press).
5.M. Shugard, J. C. Tully, and A. Nitzan, J. Chem. Phys. 66, 2534 (1977).
6.See P. J. Robinson and K. A. Holbrook, Unimolecular Reactions (Wiley‐Interscience, London, 1972) and references therein,
6.especially, R. A. Marcus and O. K. Rice, J. Phys. and Colloid Chem. 55, 894 (1951)
6.and R. A. Marcus, J. Chem. Phys. 20, 359 (1952).
7.The density of states for the solid plus adatom and total number of solid states are determined by the steepest descent method given by Robinson and Holbrook, Ref. 6, pp. 144–146. The partition functions and are the only quantities needed for and respectively, and are defined by , , , , and where is a step function. The rate appears to be a function of since both and are very strong functions of However, the ratio of becomes constant as increases. The value of used in these calculations is typically depending on and
8.The barrier height D is from R. Sau and R. P. Merrill, Surf. Sci. 34, 268 (1973)
8.and the frequency from a Morse potential of Y.‐W. Lin and G. Wolken, Int. J. Quant. Chem. “Quantum Model for Gas‐Solid Energy Transfer: Role of Phonon Polarization and Propagation Direction,” (in press).
9.M. J. Dresser, T. E. Madey, and J. T. Yates, Jr., Surf. Sci. 42, 533 (1974).
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