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Abstract
Atomic force microscopy is an imaging tool used widely in fundamental research, although it has, like other scanned probe microscopies, provided only limited information about the chemical nature of systems studied. Modification of force microscope probe tips by covalent linking of organic monolayers that terminate in well-defined functional groups enables direct probing of molecular interactions and imaging with chemical sensitivity. This new chemical force microscopy technique has been used to probe adhesion and frictional forces between distinct chemical groups in organic and aqueous solvents. Contact mechanics provide a framework to model the adhesive forces and to estimate the number of interacting molecular groups. In general, measured adhesive and frictional forces follow trends expected from the strengths of the molecular interactions, although solvation also plays an important role. Knowledge of these forces provides a basis for rationally interpretable mapping of a variety of chemical functionalities and processes such as protonation and ionization.