Intoduction Potentials Simulations Conclusions

Agrégats carbonés: avancées theoriques

Antonio Gamboa, Pascal Parneix, Cyril Falvo

ISMO

July 10, 2014

Gamboa, Parneix, Falvo Agrégats carbonés

 Intoduction Potentials Simulations Conclusions

MAIN OBJECTIVE:
Develop a program to implement
the REBO-AIREBO reactive
potential to perform different
calculations over PAH molecules
Optimizations of geometry
calculations.
Molecular Dynamics
Montecarlo, Metropolis and
Multitempering.

Gamboa, Parneix, Falvo Agrégats carbonés

 Intoduction Potentials Simulations Conclusions

Interaction Potential

The reactive empirical bond order REBO and AIREBO

potentials have proved to model propperly the C-C, C-H and
H-H interactions for different hydrocarbons.

Gamboa, Parneix, Falvo Agrégats carbonés

 Intoduction Potentials Simulations Conclusions

REBO potential

General equation
N X
X N
V = V R (rij ) + bij V A (rij )
i j>i

where V R and V A are two body repulsive and attractive

potentials, and bij is a bond order term that considers, 2, 3 and
4 body interactions.

Gamboa, Parneix, Falvo Agrégats carbonés

 Intoduction Potentials Simulations Conclusions

VA and V R
10

VR
The attractive and repulsive potentials
are given by
5

Q
V (eV)

V R (r ) = fc (r )(1 + )Ae−αr
0

r
−5

X
V A (r ) = fc (r ) Bn e−βn r
A
V
n=1,3
−10

0.5 1.0 1.5 2.0 2.5 3.0

r (A)

Gamboa, Parneix, Falvo Agrégats carbonés

 Intoduction Potentials Simulations Conclusions

Switch off function

The function f c (r ) switches off the

interaction beyond a certain distance:
5

r1 r2 
V(eV)

1 r < r1
0






 h  i
f c (r ) = 1
2 cos π rr2−r1
−r1 r1 < r < r2
−5






0 r > r2


0.5 1.0 1.5 2.0 2.5 3.0

r(A)

Gamboa, Parneix, Falvo Agrégats carbonés

 Intoduction Potentials Simulations Conclusions

Bond order term

The bond order term is a sum of

different contributions:

1  σ−π 
bij = bij + bjiσ−π + πij + bijdh
2
Where:
bijσ−π is a term that depends on
the angles θjik between
neighbours and on the
coordination numbers.

Gamboa, Parneix, Falvo Agrégats carbonés

 Intoduction Potentials Simulations Conclusions

Bond order term

The bond order term is a sum of

different contributions:
1  σ−π 
bij = bij + bjiσ−π + πij + bijdh
2
Where:
πij is a spline function that
depends on the conjugation
numbers.
bijdh is a four body correction that
depends on the dihedral angles
of the molecule.

Gamboa, Parneix, Falvo Agrégats carbonés

 Intoduction Potentials Simulations Conclusions

Airebo potential

The airebo potential is a

generalization of the rebo one that
includes:
Where:
One term that takes in account
Van der Waals interactions.
N X
X N
V LJ = f 0c VijLJ
i j>i

where VijLJ is a Lennard-Jones

type potential.
A torsional correction V tors that
depends on the dihedral angles.

Gamboa, Parneix, Falvo Agrégats carbonés

 Intoduction Potentials Simulations Conclusions

Method comparison

Gamboa, Parneix, Falvo Agrégats carbonés

 Intoduction Potentials Simulations Conclusions

Multitempering MonteCarlo

We start with a set of boxes with a definite length and a certain

number of C and H randomly distributed, and different
temperatures.
In each box, we move one atom randomly chosen. The
new j configuration is kept with a probablility given by
min(1, exp(−β(Uj − Ui ))

Each definite number of steps, one tries to interchange

configurations between two adjacent temperatures i and j,
the attempt is accepted with a probability:
min/1, exp(−(βi − βj ) ∗ (Uj − Ui ))

Gamboa, Parneix, Falvo Agrégats carbonés

Intoduction Potentials Simulations Conclusions

Gamboa, Parneix, Falvo Agrégats carbonés

 Intoduction Potentials Simulations Conclusions

Conclusions

We succeded in the developing of a program to calculate

PAH properties using the REBO-AIREBO potential.

Different comparisons of the AIREBO potential with

another more accurate models show a good dynamical
behavior in the dynamical modelization of simple PAH
molecules.

The calculation of reactivity behavior of carbon and

hidrogen atoms in a box show an interesting behaviour that
need to be explored in a deeper way.

Gamboa, Parneix, Falvo Agrégats carbonés