Strong polarization-induced reduction of addition energies in single-molecule nanojunctions

Nano Lett. 2008 Nov;8(11):3809-14. doi: 10.1021/nl8021708. Epub 2008 Oct 28.

Abstract

We address polarization-induced renormalization of molecular levels in solid-state based single-molecule transistors and focus on an organic conjugate molecule where a surprisingly large reduction of the addition energy has been observed. We have developed a scheme that combines a self-consistent solution of a quantum chemical calculation with a realistic description of the screening environment. Our results indeed show a large reduction, and we explain this to be a consequence of both (a) a reduction of the electrostatic molecular charging energy and (b) polarization induced level shifts of the HOMO and LUMO levels. Finally, we calculate the charge stability diagram and explain at a qualitative level general features observed experimentally.