Adsorption is a ubiquitous phenomenon that plays key roles in numerous applications including molecule separation, energy storage, catalysis, and lubrications. Since adsorption is sensitive to molecular details of adsorbate molecule and adsorbent materials, it is often difficult to describe theoretically. Molecular modeling capable of resolving physical processes at atomistic scales is an effective method for studying adsorption. In this dissertation, the adsorption of small molecules in three emerging materials systems: porous liquids, room-temperature ionic liquids, and atomically sharp electrodes immersed in aqueous electrolytes, are investigated to understand the physics of adsorption as well as to help design and optimize these materials systems. Thermodynamics and kinetics of gas storage in the recently synthesized porous liquids (crown-ether-substituted cage molecules dispersed in an organic solvent) were studied. Gas molecules were found to store differently in cage molecules with gas storage capacity per cage in the following order: CO2>CH4>N2. The cage molecules show selectivity of CO2 over CH4/N2 and demonstrate capability in gas separation. These studies suggest that porous liquids can be useful for CO2 capture from power plants and CH4 separation from shale gas. The effect of adsorbed water on the three-dimensional structure of ionic liquids [BMIM][Tf2N] near mica surfaces was investigated. It was shown that water, as a dielectric solvent and a molecular liquid, can alter layering and ordering of ions near mica surfaces. A three-way coupling between the self-organization of ions, the adsorption of interfacial water, and the electrification of the solid surfaces was suggested to govern the structure of ionic liquid near solid surfaces. The effects of electrode charge and surface curvature on adsorption of N2 molecules near electrodes immersed in water were studied. N2 molecules are enriched near neutral electrodes. Their enrichment is enhanced as the electrode becomes moderately charged but is reduced when the electrode becomes highly charged. Near highly charged electrodes, the amount of N2 molecules available for electrochemical reduction is an order of magnitude higher near spherical electrodes with radius ~1nm than near planar electrodes. The underlying molecular mechanisms are elucidated and their implications for development of electrodes for electrochemical reduction of N2 are discussed. / Doctor of Philosophy / Adsorption is a ubiquitous phenomenon that plays key roles in numerous applications including molecule separation, energy storage, catalysis, and lubrications. Since adsorption is sensitive to molecular details of adsorbate molecule and adsorbent materials, it is often difficult to describe theoretically. Molecular modeling capable of resolving physical processes at atomistic scales is an effective method for studying adsorption. In this dissertation, the adsorption of small molecules in three emerging materials systems: porous liquids, room-temperature ionic liquids, and atomically sharp electrodes immersed in aqueous electrolytes, are investigated to understand the physics of adsorption as well as to help design and optimize these materials systems. Thermodynamics and kinetics of gas storage in the recently synthesized porous liquids (crown-ether-substituted cage molecules dispersed in an organic solvent) were studied. Gas molecules were found to store differently in cage molecules with gas storage capacity per cage in the following order: CO2>CH4>N2. The cage molecules show selectivity of CO2 over CH4/N2 and demonstrate capability in gas separation. These studies suggest that porous liquids can be useful for CO2 capture from power plants and CH4 separation from shale gas. The effect of adsorbed water on the three-dimensional structure of ionic liquids [BMIM][Tf2N] near mica surfaces was investigated. It was shown that water, as a dielectric solvent and a molecular liquid, can alter layering and ordering of ions near mica surfaces. vi A three-way coupling between the self-organization of ions, the adsorption of interfacial water, and the electrification of the solid surfaces was suggested to govern the structure of ionic liquid near solid surfaces. The effects of electrode charge and surface curvature on adsorption of N2 molecules near electrodes immersed in water were studied. N2 molecules are enriched near neutral electrodes. Their enrichment is enhanced as the electrode becomes moderately charged but is reduced when the electrode becomes highly charged. Near highly charged electrodes, the amount of N2 molecules available for electrochemical reduction is an order of magnitude higher near spherical electrodes with radius ~1nm than near planar electrodes. The underlying molecular mechanisms are elucidated and their implications for development of electrodes for electrochemical reduction of N2 are discussed.