A fundamental study of the formation of negative hydrogen ions via surface conversion is presented. Employed is a novel type of converter, namely a pure barium metal surface. In spite of the high work function of barium compared to more conventional cesiated converters, considerable yields of negative ions were produced. Conversion efficiencies up of 4% are obtained, which is of the same order as for cesiated converters. The high negative-ion yield is probably related to the electron density of barium, which is almost twice that of cesiuim. This is confirmed by model calculations and by UHV scattering experiments under well-defined conditions. Furthermore, calculations showed that the hydrogen coverage of the converter increases with increasing flux of positive hydrogen ions to the surface. This behavior is confirmed experimentally. Seeding the hydrogen plasma with argon has no significant effect on the conversion efficiency. This is believed to be related to the competition between the lowering of the surface hydrogen coverage and the increase of the hydrogen desorption rate, both due to the higher sputter coefficient of argon compared to hydrogen.