Interaction between adatoms on graphene:

towards a model for nanocluster nucleation

Riccardo Sabatini1,2, Stefano Ave3 and Maria Peressi2,3
1SISSA, 2 CNR-INFM

Democritos National Simulation Center, 3 University of Trieste - Italy Center, - project NANOCAT funded by Regione Friuli Venezia Giulia -

A limited number of full ab-initio calculations of atoms adsorbed individually or in pair on graphene, provides informations about adsorbate-substrate and adsorbate-adsorbate interactions, with the aim of exctrating a model potential to simulate nanoclusters. Preliminar results are shown for K, Pt, Pd, Ru and Rh adatoms.

Computational approach
QUANTUM ESPRESSO (http://www.quantum-espresso.org/) Density Functional Theory - pseudopotentials
(LDA for K on graphene; GGA for all the other cases)

Lateral interactions between adatoms

Lateral interations can be obtained by calculating the energy of one pair of adsorbed atoms in a 3x3 cell contained in a 6x6 cell (lateral interaction within the pair is dominant w.r.t. images).

Adsorption energies
Eads. single atom = Etot - (Egraphene + E isolated atom )
Eads (eV)
Lattice paramter a = 2.46

Some selected pairs of adsorbed atoms within a 3x3 cell

Elat = Etot - Egraphene - 2 (Eisolated atom+ Eads. single atom )

Elatt (eV)

K
Eads. single atom

Graphene unit cell: 2 C atoms 3 inequivalent adsorption sites: H - hollow (1 for each unit cell) T - top on C atoms (2 sites in the unit cell) B - bridge (3 sites in the unit cell) H site is favored for K, Rh, Ru; slightly unfavored for Pd and Pt; B and T are similar in energy K is unbound w.r.t. graphene for a coverage of 0.5. This is remarkably different from the other atoms (but atomic radii are rather different: r(K)=2.35 , r(others)1.35 ) Ru is strongly bound. Since for n>1 the difference of Eadsfor H, T and B is independent on n, this suggest that lateral interactions should be site-independent.

Calculations have been performed for several pairs, which differ by adsorption sites or by orientation of the pair axis w.r.t. the graphene sheet. For the configurations tested in the present work (others are in progress), with the exception of atoms coadsorbed very closely (interatomic distance ~ a), lateral interations depend only on distance (neither on orientation nor on the type of the adsorption sites). Therefore, such interaction can be easily fit by a simple isotropic form depending only on the adsorbed species for r>a, i.e. also in a range where it is sizeable (3-5 ).

Pd
Eads. single atom

Pt
Eads. single atom Eads. single atom

Rh
Eads. single atom

Ru
Eads. single atom

Lateral interaction are always positive (repulsive) for K, negative for the other atoms considered here. The e!ective interatomic potential derived from these results, together with a few Interatomic distance () relevant di!usion, aggregation and disaggregation barriers Interatomic lateral energy (in eV) between atoms adsorbed on different calculated on small nanoclusters, can be used for a sites and at different distances. simple atomistic model to study The adsorption energy of a single the nucleation of more complex atom (blue line) and the optimized distance (F.c.- Free cluster- length) nanoclusters.
of an isolated pair in vacuum are reported for comparison.

Adsorption energy (in eV) for a single adsorbed atom in a nxn graphene cell, corresponding to a coverage of 1/(2n). In the inset the value in a 6x6 cell (i.e., when lateral interactions are negligible) is reported on the same scale for immediate comparison between the different atomic species.