Chemisorption of hydrogen on Pd{111} is a relatively simple, yet important surface chemical process. By using low-temperature scanning tunneling microscopy, tip-induced motion of adsorbed atomic hydrogen at 4 K has been observed at low coverage. The motion has been ascribed to excitation of vibrational modes that decay into translational modes; vibrational spectroscopy via inelastic electron tunneling corroborates this assignment, and the barrier to hydrogen atom motion has been determined. At higher coverages, tip-induced motion of vacancies in the hydrogen overlayer is observed, and the associated barrier has also been determined.