The formation of a tribologically reliable interface between the magnetic recording disk and the magnetic recording head in hard-disk drives is predicated upon the presence of a molecularly thin perfluoropolyether (PFPE lubricant film. The molecular interactions that develop between the PFPE lubricant and the underlying amorphous carbon overcoat of the magnetic recording disk govern the adhesion, physical coverage, thermal stability, and mobility of the lubricant on the carbon surface and hence are of paramount importance in defining the tribological performance of the drive. In this work, information pertaining to the interfacial interactions between the hydroxyl-terminated PFPE lubricant Zdol and amorphous carbon surfaces is obtained via ab initio calculations. The small fluorinated ether molecules CF3OCF2CH2OH (ZD) and CF3OCF3 (PFDME) were used as computationally tractable models for the PFPE lubricants. A population analysis is performed on the ZD model lubricant and the various chemical functionalities known to exist on amorphous carbon surfaces. In the case of an amorphous, hydrogenated carbon surface, CHx, the adhesive interactions of the PFPE backbone with the nonpolar component of the carbon surface were modeled by the interaction of ZD with simple hydrocarbons. The attractive van der Waals interactions that result are comparatively weak and insufficient at room temperature to overcome the associated decrease in entropy. As a consequence, these interactions will not contribute significantly to the adhesion of PFPE＇s to the carbon surfaces under disk-drive operating conditions. The primary source of adhesion in the Zdol CHx system stems from hydrogen bonding of the hydroxyl end groups of the Zdol lubricant with the carboxylic acid and ketone functionalities on the CHx surface. The computed binding energies of the ZD + ketone and ZD + carboxylic acid interactions are -11 and -15 kcal/mol, respectively. These interaction strengths are large enough to compensate for the entropy decrease and hence result in a net decrease in the free energy. In addition to these thermodynamically stable adhesive interactions, the computed binding energy of the cohesive hydrogen-bonding interactions between ZD molecules is significant. The formation of a highly associated, two-dimensional structure is therefore possible for molecularly thin Zdol films on carbon surfaces. Amorphous nitrogenated carbon, CNx, can also provide strong physisorption sites for Zdol. The interaction of ZD with imine and nitrile functionalities were studied. The interactions of the hydroxyl end group with imine centers is strongly attractive, leading to the formation of a hydrogen bond with a strength of -16 kcal/mol. Interactions with nitrile sites are somewhat less favorable with a computed binding energy of -10 kcal/mol. The nitrogen centers on CNx are negatively charged, and hence repulsive interactions with the negatively charged perfluoroalkyl ether backbone are expected. The modeling results are then used to interpret previous experimental results, and a detailed picture of the fundamental interactions that occur between PFPE＇s and carbon surfaces emerges.