Polymers and molecular solids: New frontiers in surface science

A brief review is given of the present state of knowledge of the surface properties of polymers and molecular solids. These materials are shown to exhibit surface phenomena which are dramatically different from those characteristic of metals and covalent solids. The origin of these differences resides in the combined occurrence both of large electronic and atomic polarizabilities and of small probabilities for the transfer of an electronic excitation from one molecular site to another. The interplay of these two quantities leads to a diversity in the character of the resulting electronic excitations, ranging from localized molecular ion states in aromatic pendant-group polymers to quasi-one-dimensional metallic behavior in certain charge transfer salts and polymers. The primary role of the surface in such materials is the introduction of large, inhomogeneous fluctuations in the relaxation energies associated with the polarization of the solid by an excitation. These fluctuations produce a number of novel phenomena including localized surface states in the absence of dangling bonds, inhomogeneous broadening of photo-emission spectra, and alterations of the charge state of surface molecules. A simple, unified theoretical framework is developed for the interpretation of these phenomena.