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

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 molecul...

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Detalles Bibliográficos
Autores: Foti, G. (Giuseppe)|||/items/4672402f-04d7-471b-9233-8d5edfade2d0, Vázquez, H. (Hector)|||/items/b14e6046-8d1c-46e8-b9d7-42cebffc7dc4
Tipo de recurso: artículo
Fecha de publicación:2016
País:España
Institución:Universidad de Navarra
Repositorio:Dadun. Depósito Académico Digital de la Universidad de Navarra
Idioma:inglés
OAI Identifier:oai:dadun.unav.edu:10171/111169
Acceso en línea:https://hdl.handle.net/10171/111169
Access Level:acceso abierto
Palabra clave:Single molecule transport
N-heterocyclic carbene
Tip-induced gating
DFT-NEGF
Metal-molecule charge rearrangement
Descripción
Sumario: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.