Environmental Engineering Reference
In-Depth Information
=
a volume V
L x L y L z . Charges interact according to Coulomb's law and the total
electrostatic energy for the periodic system is given by
i
1
4 ˀʵ 0 ʵ r
q i q j
r N
,
U
(
) =
(10)
|
r ij + (
n x L x ,
n y L y ,
n z L z ) |
j > i
n x
n y
n z
where n
and n z are non-negative integer numbers, and
ʵ 0 and ʵ r are the dielectric constants of vacuum and water at room temperature,
respectively. According to Ewald's approach it is convenient to separate this long-
range electrostatic interaction into real and reciprocal space, getting a short-ranged
sum which may be written as
= (
n x ,
n y ,
n z )
, n x ,
n y ,
1
4 ˀʵ 0 ʵ r
erfc
ʵ r
)
r N
U
(
) =
q i q j
r
j > i
i
N
q i 2
2 V
ʱ ʵ
ˀ
+
Q
(
k
)
S
(
k
)
S
(
k
)
,
(11)
k
=
0
i
=
1
with
e k 2
2
ʵ
N
/
4 ʱ
2 L (
q i e i k · r ij
Q
(
k
) =
,
S
(
k
) =
,
k
=
m x ,
m y ,
m z ).
k 2
i
=
1
Here, ʱ ʵ is the parameter that controls the contribution of the real space, k is the
magnitude of the reciprocal vector k , m x ,
)
is the complementary error function (cf. Mayoral and Nahmad-Achar 2012 ). Equa-
tion ( 11 ) is a good approach to 1
m y ,
m z are integer numbers, and erfc
ʵ r
/
r including the full long-range characteristic of
electrostatic interactions.
In the DPD approach the conservative force F c is mathematically well defined
at r
0, making possible the overlap between particles, but the electrostatic con-
tribution diverges at r
=
0, giving rise to non-natural ionic pairs. A solution of
this problem was proposed by Groot ( 2003 ) by using charge distributions on DPD
particles such as a Slater-type charge density distribution expressed as:
=
q
ˀʻ
3 e 2 r ,
ˁ(
r
) =
(12)
where ʻ is the decay length of the charge. For this distribution, well-known approx-
imated expressions for the force are available. The reduced interaction potential
between two charged distributions separated by a distance r
from center to center
is given by:
4 ˀ u (
r )
Z i Z j
r
e 2 ʲ r
+ ʲ r )
=
[
1
(
1
] ,
(13)
ʓ
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