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Email: RSadus@swin.edu.au
• Many effective potentials have been developed (Maitland et al., 1981) and
applied to atoms. Historically, an empirical approach was used with the
parameters of the potential being obtained from experimental data such as
second virial coefficients, viscosities, molecular beam cross sections etc.
Conclusions regarding the accuracy of pair potential were made by comparing
the properties predicted by the potential with experiment.
• Effective potentials for atoms are often incorporated into the molecular
simulation of platonic molecules and increasingly, macromolecules.
Therefore, the atomic pair potential is an important starting basis for predicting
molecular properties.
∞
r ≤σ
u( r) = εσ r
−
r exp − z σ − 1 r >σ
m −n n −m
u(r) = ε x − x
n − m n − m
σ 12 σ 6
4ε − +ε r ≤ 21/6σ
u(r) = r r
0 r > 21/6σ
∞ r ≤d
u(r) = σ −d 12 σ −d 6
4ε r − d − r −d r >d
∞ r ≤ λrm
6 r rm 6
u(r) = ε
exp α 1− − r > λrm
1− 6 α rm r
α
λ 7 exp [α (1 − λ )] − 1 = 0
5 2
C
u(r) = ε ∑Ai (x −1) exp[α(1− x)] − ∑ 2 j +26j +6
i
i =0 j =0 δ + x
In the BFW potential, x = r/rm and the other parameters are obtained
by fitting the potential to experimental data for molecular beam
scattering, second virial coefficients, and long-range interaction
coefficients. The contribution from repulsion has an exponential-
dependence on intermolecular separation and the contribution to
dispersion of the C6, C8 and C10 coefficients are included.
u ( r ) = a1 exp[ − a 2 (r / a 0 ) 2 ] + a 3 exp[ − a 4 (r / a 0 ) 2 ]
+ a 5 exp[ − a 6 (r / a 0 ) 2 ] + a 7 (r / a 0 ) − 10 + a 8 (r / a 0 ) −8 + a 7 (r / a 0 ) −6
where a0 is the Bohr radius and the remaining parameters do not have
any physical meaning.
R. J. Sadus, Centre for Molecular Simulation, Swinburne University of Technology 19
Ab Initio Potentials (contd)
qa qb
u ( q, q )
(r) =
r
qaµb cosθb
u(q ,µ )(r) = −
r2
R. J. Sadus, Centre for Molecular Simulation, Swinburne University of Technology 21
Ionic and Polar Potentials (contd)
3µaQb
u(µ,Q) (r) =
4
cosθa (3cos2
θb −1) −2sinθa sinθb cosθb cos(φa −φb )
4r
3QQ
u(QQ
, )
(r) = a b
5
1−5cos2
θa −5cos2
θb −15cos2
θa cos2
θb + 2[sinθa sinθb cos(φa −φb ) −4cosθa cosθb ]2
16r
At this stage it should be noted that most of the above interactions are
long-ranged and as such special techniques described below are
required otherwise the minimum image convention would be violated.
E(r, l,θ ,τ ,χ ) = ∑u
nonbonds
nb (r) + ∑ ub (l) +
bonds
∑ u (θ) + ∑ u (τ ) + ∑
bending
θ
dihedral
τ
out−of − plane
uχ (χ) + ∑uel + ...
where unb is the non-bonded potential, ub is the bond potential, uθ is the bond
angle potential, uτ is the torsional potential, uχ is the out-of-plane bending
(improper torsional) potential, and uel is the Coulombic potential. This
equation only includes “diagonal terms” but it can be extended to include
contributions from “cross terms” such as bond-angle or angle-angle
interactions.
R. J. Sadus, Centre for Molecular Simulation, Swinburne University of Technology 24
Molecular Force Fields (contd)
Vn σ
12
σ ij
6
+ ∑ ∑ 2
[1 + cos( nτ − γ ) ] + ∑ 4ε i j ij
rij
−
rij
dihedrals n i< j
1 1,4 terms σ
12
σ ij
6
C ij D ij
+ ∑ ij
ri j
−
rij +
∑ r 12 − r 10
vdW scale i< j
H − bonds
ij ij
1,4 terms
qi q j 1 qi q j
+∑ + ∑
i< j ε rij EE scale i< j D rij
1.5
1.0
0.5
0.0
-0.5
-1.0
-1.5
0 1 2 3 4 5
Comparison of the decay of (a) Coulombic (qaqb/εσ = 1), (b) Stockmayer (µaµb/εσ3 =
1, θa = 90º, θb = 90º and φa = φb), and (c) Lennard-Jones (u/ ε) reduced potentials
(u*), as a function of reduced intermolecular separation (r* = r/σ).
R. J. Sadus, Centre for Molecular Simulation, Swinburne University of Technology 27
Long Range Interactions (contd)
E(short)i = ∑ u(r )
j ;r ≤ rc
ij
where µi is the dipole moment of the central molecule and µj is the dipole
moment of neighbouring molecules within the sphere. Consequently, the total
energy experienced by each molecule is evaluated from:
Ei = E(short)i + E(long)i
1 rij < rt
r −r
f ( rij ) = c ij rt ≤ rij ≤ rc
rc − rt
0 rc < rij
where rt = 0.95rc.
R. J. Sadus, Centre for Molecular Simulation, Swinburne University of Technology 30
Long Range Interactions (contd)