Journal of Physical Chemistry, Vol.99, No.35, 13213-13216, 1995
Semiempirical Calculations and Scanning Probe Microscopy Studies of Polythiophene Thin-Films
Electrochemically prepared films of polythiophene were studied using the technique of noncontact scanning probe microscopy. Images of the film surfaces revealed many polymer strands atop the bulk film surface. The average diameter of these strands was 9-15 +/- 2 Angstrom, indicating a coil or helical structure. The substructure of the bulk film surface was not resolvable, likely indicating a close-packed structure of (planar) polymer chains. Semiempirical AM1 calculations on isolated bithiophene and terthiophene oligomers indicate minima at torsional angles of 35 degrees and 153 degrees for bithiophene and combinations of these torsional angles for terthiophene. These calculations show the energetic feasibility of a nonplanar, syn-like thiophene molecular conformation on the film surface, where interactions with neighboring polythiophene are minimized. Geometry-optimized AM1 calculations were also performed for hydrated bithiophene. We show that partial orientation of the polar water molecules in the neighborhood of the bithiophene oligomer alters the energetics of torsion angle rotation for this molecule. Torsion angle minima were found to be at 0 degrees and 180 degrees, with the relative potential barrier between these conformations reduced with respect to the isolated case.