Tip-induced gating of molecular levels in carbene-based junctions

0462283 - FZÚ 2017 RIV GB eng J - Journal Article
Foti, Giuseppe - Vázquez, Héctor
Tip-induced gating of molecular levels in carbene-based junctions.
Nanotechnology. Roč. 27, č. 12 (2016), 1-8, č. článku 125702. ISSN 0957-4484. E-ISSN 1361-6528
R&D Projects: GA ČR GA15-19672S
Institutional support: RVO:68378271
Keywords : single molecule transport * N-heterocyclic carbene * tip-induced gating * DFT-NEGF * metal-molecule charge rearrangement
Subject RIV: BM - Solid Matter Physics ; Magnetism
Impact factor: 3.440, year: 2016

We study the conductance of N-heterocyclic carbene-based (NHC) molecules on gold by means of first-principles calculations based on density-functional theory and non-equilibrium Green's functions. We consider several tip structures and find a strong dependence of the position of the NHC molecular levels with the atomistic structure of the tip. The position of the lowest unoccupied molecular orbital (LUMO) can change by almost 0.8 eV with tip shape. Through an analysis of the net charge transfer, electron redistribution and work function for each tip structure, we rationalize the LUMO shifts in terms of the sum of the work function and the maximum electrostatic potential arising from charge rearrangement. These differences in the LUMO position, effectively gating the molecular levels, result in large conductance variations. These findings open the way to modulating the conductance of NHC-based molecular circuits through the controlled design of the tip atomistic structure.
Permanent Link: http://hdl.handle.net/11104/0261754