We report the first measurements of internal energy distributions of the OH produced via a direct mechanism, isolated from other components on the basis of time-of-flight, in the interfacial reaction between gas-phase O(3P) atoms and the liquid hydrocarbon squalane, C30H62. O( 3P) atoms were generated by laser photolysis of NO2 above the liquid. Resulting hydroxyl radicals that escape from the surface were detected by laser-induced fluorescence. Time-of-flight profiles demonstrate that the kinetic energy of the fastest OH (v' = 1) is lower than that of (v' = 0). Rotational distributions were measured at the rising edge of their appearance for both OH (v' = 0) and (v' = 1). They were found to differ substantially more than at the peak of their profiles. They were also less dependent on the bulk liquid temperature. We conclude that the new data confirm strongly that at least two mechanisms contribute to the production of OH. The higher-velocity component has translational and rotational energy distributions, observed cleanly for the first time, consistent with a direct mechanism. The close correspondence of these rotational distributions to those from the corresponding homogeneous gas-phase reaction of O(3P) with smaller hydrocarbons suggests a very similar, near collinear direct abstraction. This is accompanied by a slower component with kinetic energy and rotational (but not vibrational) distributions reflecting the temperature of the liquid, consistent with a distinct trapping-desorption mechanism. © 2006 American Chemical Society.