ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
We have determined the dependence of the dissociative adsorption probability in the zero coverage limit, S0, for H2 on Cu(111) as a function of translational energy, Ei, and incidence angle, θi, vibrational state, v, and rotational state, J. We have also obtained information on the effect of surface temperature, Ts, on this probability. These results have been obtained by combining the findings of two separate experiments. We have obtained the form of the dependence of S0 on Ei at Ts=925 K for a range of quantum states from desorption experiments via the principle of detailed balance. We have obtained absolute S0 values from direct molecular beam adsorption experiments, which reveal that S0 scales with the so-called "normal energy,'' En=Ei cos2 θi. The desorption experiments provide detailed information for J=0 to 10 of H2(v=0) and for J=0 to 7 of H2(v=1). The beam experiments additionally provide information on the adsorption of H2(v=2), averaged over J. All measurements are consistent with adsorption functions with an s-shaped form, which can be described by S0=A(1+erf(x))/2, where x=(En−E0)/W. Values of W are ∼0.16 and 0.13 eV for v=0 and v=1, respectively, at Ts=925 K, falling by about 0.05 eV for Ts=120 K, and with only a slight dependence on J. Values of A are insensitive to v and J, with a value of ∼0.25. S(En,v,J) curves are thus similar for different v and J, but shifted in En.In contrast, we find that the values of E0, which determine the mid-point of the curves, have a strong dependence on v and J. Specifically, E0 for H2(v=0) molecules is about 0.6 eV, falling to 0.3 and 0.1 eV for H2(v=1) and H2(v=2), respectively. Translational energy is thus about twice as effective as vibrational energy in promoting dissociation. E0 rises with increasing J at low J, before falling at high J, indicating that rotational motion hinders adsorption for low rotational states (J〈4), and enhances adsorption for high rotational states (J(approximately-greater-than)4). Results are compared with similar studies on the D2/Cu(111) system and with recent calculations. Finally, these results are used to predict the dependence of the rate of dissociation on temperature for a "bulb'' experiment with ambient hydrogen gas in contact with a Cu(111) surface. This simulation yields an activation energy of 0.47 eV for temperatures close to 800 K, compared to a literature value of 0.4 eV from experiment. Analysis of the temperature dependence reveals that the dominant reason for the increase in rate at high temperature is the increase in population of the high energy tail of the translational energy distribution. © 1995 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.469511
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