Premium
Combined molecular and periodic DFT analysis of the adsorption of co macrocycles on graphene
Author(s) -
Calborean Adrian,
Morari Cristian,
Maldivi Pascale
Publication year - 2018
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25093
Subject(s) - graphene , density functional theory , bilayer graphene , materials science , monolayer , molecule , dopant , chemical physics , doping , conjugated system , porphyrin , adsorption , fermi level , computational chemistry , nanotechnology , chemistry , photochemistry , organic chemistry , physics , quantum mechanics , optoelectronics , polymer , electron , composite material
The molecular doping of graphene with π‐stacked conjugated molecules has been widely studied during the last 10 years, both experimentally or using first‐principle calculations, mainly with strongly acceptor or donor molecules. Macrocyclic metal complexes have been far less studied and their behavior on graphene is less clear‐cut. The present density functional theory study of cobalt porphyrin and phthalocyanine adsorbed on monolayer or bilayer graphene allows to compare the outcomes of two models, either a finite‐sized flake of graphene or an infinite 2D material using periodic calculations. The electronic structures yielded by both models are compared, with a focus on the density of states around the Fermi level. Apart from the crucial choice of calculation conditions, this investigation also shows that unlike strongly donating or accepting organic dopants, these macrocycles do not induce a significant doping of the graphene sheet and that a finite size model of graphene flake may be confidently used for most modeling purposes. © 2017 Wiley Periodicals, Inc.