State-selected molecular-beam reaction dynamics of K with HF (υ = 1, j = 5, 6 and 7)

Abstract

The crossed-molecular-beam method has been used to measure relative integral cross sections σ r (υ = 1, j; E) of the endothermic (0.75 eV) reaction K + HF (υ = 1, j) → KF + H as a function of both the rotational quantum number j ( j = 5, 6 and 7) and the translational energy E (0.55 ⩽ E ⩽ 1.32 eV) of the reagents. The vibrational-rotational (υ, j) states of HF were populated by infrared pumping with the radiation of a properly tuned pulsed chemical HF laser. In addition, relative cross sections with υ = 0 but averaged with respect to the initial rotational-state distribution of the HF molecules were also determined. The results exhibit three remarkable features: (a) σ r (υ = 1, j; E) rises with increasing j, (b) the steepness of the ascent roughly decreases with increasing E, (c) at E = 0.98 eV reagent vibrational energy is about a factor of 200 more efficient in promoting the reaction than reagent translational energy. An intuitive dynamical model suggests that observations (a) and (b) are to be expected for a reaction governed by a potential-energy surface with a late barrier. This is consistent with the well-known interpretation of large vibrational effects as indicated by result (c).