We report a theoretical study of single molecule conduction switching of photochromic dithienylethene molecules. The light-induced intramolecular transformation drives a swapping of the highest occupied molecular orbital and lowest unoccupied molecular orbital between two distinct conjugated paths. The shuffling of single and double bonds produces a significant conductance change when the molecule is sandwiched between metal electrodes. We model the switching event using quantum molecular dynamics and the conductance changes using Green’s function electronic transport theory. We find large on-off conductance ratios (between 10 and over 100) depending on the side group outside the switching core.

• Received 19 December 2003

DOI:https://doi.org/10.1103/PhysRevLett.93.248302