Helium-3 surface spin echo spectroscopy (HeSE) has been used to measure the diffusive dynamics of adsorbates on close-packed metal surfaces, namely hydrogen on Cu(111), Pd(111) and Ru(0001), carbon and oxygen on Ru(0001), and oxygen on Cu(111). Chapter 2 reviews the HeSE technique and describes the relevant dynamical models and statistical methods used to interpret data in later chapters. The performance of the ionizing detector is analysed, with a focus on the signal-to-noise ratio.

In Chapter 3 expressions for the classical intermediate scattering function (ISF) are introduced for open and closed systems. The effects of corrugation and surface-perpendicular motion on the amplitude of different components in the ISF are modelled analytically and compared with simulation. The exact ISF for a particle on a flat surface, obeying the Generalized Langevin Equation with exponential memory friction, is calculated analytically. In Chapter 4 the analytical ISF is calculated for quantum Brownian motion and for coherent tunneling dynamics in a tight binding system. The bounce method for calculating quantum mechanical hopping rates in dissipative systems is applied to model diffusion of hydrogen on Ru(0001).

Chapter 5 presents the first HeSE measurements of carbon and oxygen diffusion. C/Ru(0001) diffusion is assigned to a small carbon cluster. The jump rate has an activation energy $EA=292\pm 7$meV in the temperature range $550K\le T\le 1300$K. Oxygen diffusion is significantly slower. By comparison of literature data with the new HeSE results, the activation energy for oxygen diffusion at low coverage is estimated as $650\pm 10$meV. Oxygen measurements at high coverage $\theta \approx 0.22$ML are consistent with strong mutual O-O interactions. Surface diffusion is also observed after exposing Cu(111) to oxygen.

Chapter 6 presents low-coverage measurements of protium (H) and deuterium (D) diffusion on Ru(0001), Pd(111) and Cu(111). In the quantum activated regime there is evidence for multiple jumps in all three systems, suggesting a low dynamical friction. The measurements on Ru(0001) indicate that the deep tunneling rate is much slower for D than for H.