The interactions of a hydrogenated silicon nanodot, Si 35 H 36 , containing surface SiH and SiH 2 surface hydrides, with three representative small polar molecules, ethanol, NH 3 , and H 2 O were comparatively studied using a self-consistent charge density-functional tight-binding method, complemented by an empirical van der Waals force correction. The binding energy of ethanol with the hydrogenated silicon dot was determined to be 0.39-0.78 eV with a positive sign, indicating that this adsorption process is endothermic and thermodynamically unfavorable. In contrast, the binding energies of H 2 O and NH 3 were found to be about 0.15-0.53 eV with a negative sign, revealing exothermic and thermodynamically favorable reactions. Interestingly, these adsorptions are facilitated by H. . . H attraction, rather than by H. . . O or H. . . N H-bonding. The binding is mostly electrostatic and physical, with very little charge transfer occurring. All these adsorptions result in relatively small redshifts in optical absorption and emission spectra, according to additional time-dependent calculations, with little change in the IR peak position of their adsorbents and an almost perfect silicon surface.