The adsorption of CO on Rh(100) has been investigated as a function of temp. and CO pressure, with reflection absorption IR spectroscopy (RAIRA), LEED, and thermal desorption spectroscopy (TDS). At low coverages, most CO adsorbs linearly, up to 0.5 monolayers (ML), where a c(2*2) LEED pattern is obsd. The satn. coverage at 300 K is 0.75 ML, assocd. with p(4?2*?2)R45 Deg LEED pattern, and adsorption of CO in at least three states, namely two linear modes and one bridged mode. At temps. well below 300 K and relatively high exposures, CO is compressed into a dense hexagonal overlayer structure with a c(6*2) LEED pattern and a satn. coverage of 0.83 ML, in which the majority of the CO is bonded linearly. The activation energy of desorption for ...