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The adsorption of $CO_2$ on the $Fe_3$$O_4$(001)-($\sqrt{2}$ $\times$$\sqrt{2}$)R45{\deg} surface was studied experimentally using temperatureprogrammed desorption (TPD), electron spectroscopies (UPS and XPS), andscanning tunneling microscopy (STM). $CO_2$ binds most strongly at defectsrelated to Fe2+ including antiphase domain boundaries in the surfacereconstruction and above incorporated Fe interstitials. On the pristinesurface, $CO_2$ adsorbs molecularly at fivefold-coordinated Fe3+ sites with abinding energy of 0.4 eV. Above a coverage of 4 molecules per ($\sqrt{2}$$\times$ $\sqrt{2}$)R45{\deg} unit cell, further adsorption results in acompression of the first monolayer up to a density approaching that of a $CO_2$ice layer. Surprisingly, desorption of the second monolayer occurs at a lowertemperature ($\approx$ 84 K) than $CO_2$ multilayers ($\approx$ 88 K),suggestive of a metastable phase or diffusion-limited island growth. The paperalso discusses design considerations for a vacuum system optimized to study thesurface chemistry of metal oxide single crystals, including the calibration andcharacterisation of a molecular beam source for quantitative TPD measurements.

A Multi-Technique Study of $CO_2$ Adsorption on $Fe_3$$O_4$ Magnetite