Electron emission spectra of thermal collisions of He metastable atoms with Au(111) and Pt(111) surfaces: Evidence for Penning ionization

Electron emission spectra obtained by thermal collisions of He*(2{sup 1}S and 2{sup 3}S) atoms with Au(111) and Pt(111) surfaces were measured to clarify the electronically excited atom-metal interactions. It has been recognized that the metastable atoms de-excite on ordinary noble- and transition-metal surfaces via resonance ionization (RI) followed by Auger neutralization (AN) without no indication of Penning ionization (PI). Our data show that this traditional criterion partially breaks down in the He*-Au(111) collision system. The local electronic states near the surface were examined by first-principles calculations using density functional theory. It reveals that the itinerant sp states are significantly spilled out toward the vacuum compared to the localized 5d states, and their asymptotic features play a crucial role in determining the branching ratio between PI and RI+AN.