Photodissociation of HBr on the surface of Ar n clusters at 193 nm

Abstract

Photodissociation experiments are carried out for single HBr molecules absorbed on the surface of large Ar n clusters with the average size of 〈 n〉 = 159 at the dissociation wavelength of 193 nm. The kinetic energy of the H atom fragments is measured exhibiting peaks at zero and two energies which mark completely caged and unperturbed fragments going into the two spin orbit channels of Br, respectively. The results are compared with Molecular Dynamics simulations which account for the quantum librational delocalization of the H atom in the HBr molecule and the substitutional surface position of the molecule at 27 K. The latter result is obtained from a trajectory study of the pick-up process under realistic conditions. Both channels are populated by mainly perpendicular transitions in agreement with the results for the bare molecule. The high intensity close to the energy of the excited Br ∗ state mainly originates from slowed down dissociation products from the ground state. Calculations based on these realistic initial state conditions give also good agreement with the experimental results for the dissociation wavelength of 243 nm.