The orientational dependence of the scattering of hexapole-focused, oriented molecule beams of six symmetric-top molecules (CH3Cl, CH3F, CHCl3, CHF3, t-BuCl, CH3CN) and CH3OH from the (0001) surface of a graphite crystal is reported. Experimental angular distribution data are well represented by a two-component model, consisting of a ‘‘trapped/desorbed’’ and a ‘‘direct’’ scattered contribution. The steric effect, defined as the difference (‘‘heads’’ vs ‘‘tails’’) divided by the average of the scattered signals, has been measured as a function of the scattering angle and the degree of orientation of the molecules. There is considerable diversity among the different molecules with respect to the direction and magnitude of the steric effect of the scattering (and trapping). In all cases, however, the magnitude of the steric effect is essentially a linear function of the degree of orientation. Limited data on the incident energy dependence of the angular distributions and the steric effect are also presented. A model which deconvolutes the steric effect for the trapped/desorbed and directly scattered components is introduced. It also provides an independent estimate of the trapping probability of the incident molecules.

The scattering of focused beams of hexapole-oriented t-BuCl and CHF3 molecules from a graphite (0001) surface has been studied over the surface temperature range 165 < Ts<730 K. The detected number densities of the surface-scattered beams are compared for parallel vs antiparallel incident orientation of the molecular dipole with respect to the surface normal. From the fractional difference in scattered signals, i.e., the so-called steric effect, and from the scattering angular distributions of the unoriented molecules, the relative difference in scattering probabilities for opposite molecular orientations is obtained. For both molecules the magnitude of the relative difference in scattering (the steric effect) increases as Ts decreases. At the lowest surface temperature of 165 K the relative difference in scattering probability reaches +1.5 for t-BuCl (and −0.8 for CHF3), approaching the largest possible magnitude of 2.0, as compared to +0.3 (and −0.4 for CHF3) at the highest temperatures. At all temperatures the steric effect for directly (near-specularly) scattered molecules depends linearly on the degree of molecular orientation. From the angular distribution measurements, it is found that the inelastic translational energy loss in the ‘‘direct’’ scattering process increases as Ts decreases. Finally, the temperature dependence of the scattering probability of unoriented beams of t-BuCl and CHF3 has been obtained.

As a result of observations made by Shaw (M.S. thesis, Cornell University, 1964) in the mid-1960s, alkali rf discharges are known to operate in two spectral modes, the so-called ring mode and the red mode. Experience has shown that the ring mode is best for discharge lamps used in quantum-electronic devices such as atomic clocks and optically pumped magnetometers and that the performance of these devices seriously degrades when the lamp operates in the red mode. Understanding the origin of these modes therefore has application to understanding and improving various quantum-electronic devices. Here we show that Shaw’s model for these modes is inconsistent with observation, and we propose an alternate model based on the role of radiation trapping in multistep ionization.

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Inversion of gas-surface scattering data for potential determination using functional sensitivity analysis. I. A case study for the He-Xe/C(0001) potential J. Chem. Phys. 94, 2305 (1991); 10.1063/1.459902Orientational dependence of the translational energy transfer in the scattering of oriented fluoroform and t e r t butyl chloride molecules by a graphite(0001) surface