charge-charge, charge-dipole, dipole-charge, dipole-dipole interaction

Masahiro Yamamoto
Department of Energy and Hydrocarbon Chemistry,
Graduate School of Engineering, Kyoto University, Kyoto 606-8501, Japan
(Dated: December 1, 2008)

In the bulk and at the interface of polar solvents and/or ionic liquids, molecules feel the strong electric field and
this strong field distort the electron cloud of molecule and induces dipole around atoms. To consider this polarization
effect we should consider charge-charge, charge-dipole, dipole-charge, dipole-dipole interaction.

I. CHARGE-CHARGE (C-C) INTERACTION

The coulomb potential φ from the point charge zi e at ri is given by

0 . 2

0 . 4

0 . 6

0 . 8

1 0

1 0

1 0

1 0

FIG. 1: Coulomb potential of negative charge

zi e 1
φC (|r − ri |) = (1)
4πϵ0 |r − ri |
The electric field is given by the gradient of the potential
zi e r − ri
EiC (r) = −∇φC (|r − ri |) = (2)
4πϵ0 |r − ri |3
If we put the other point charge zj e at at rj the electrostatic energy Vcc is given by

zi zj e2 1
Vcc = zj eφC (|rj − ri |) = (3)
4πϵ0 |ri − rj |

II. CHARGE-DIPOLE (C-D) INTERACTION

In this interaction we consider two cases, i.e. (I) the coulomb potential interact with dipole µ
⃗ j = ezj pj and (II)
dipole field interact with point charge.
In the case of (I), the C-D interaction becomes
zi (−zj )e2 1 zi zj e2 1
Vcd = + (4)
4πϵ0 |rj − ri | 4πϵ0 |rj + pj − ri |
rj − ri ≡ rji , |rji | = rji , (1 + x)−1/2 ≅ 1 − x/2 + 3x2 /8... (5)
  " #
zi zj e2  1 1 =− zi zj e2
1
Vcd = − −q 1−
4πϵ0 rji r2 + 2r · p + p2 4πϵ0 rji (1 + 2rji · pj /rji
2 + p2 /r 2 )1/2
j ji
ji ji j j
 2

dipole
j

charge field
+ i

charge
+ j

dipole field

FIG. 2: charge-dipole(C-D) and dipole-charge(D-C) interaction

" #
zi zj e2 1 2rji · pj 1 p2j 3
≅ − 1−1+ 2 + 2 − 8 (2rji · pj /rji + pj /rji )
2 2 2 2
(6)
4πϵ0 rji 2 rji 2 rji
if we assume rji >> pj
zi zj e2 rji · pj zi zj e2 rij · pj zi e rij · µ
⃗j
Vcd = − 3 = 3 = 3 , ⃗ j ≡ zj epj
µ (7)
4πϵ0 rji 4πϵ0 rij 4πϵ0 rij

In the ordinary method the potential is given by −⃗

µ · EC
zi e r − ri
EiC (r) = −∇φC (|r − ri |) = (8)
4πϵ0 |r − ri |3
zi e rji · µ
⃗j zi e rij · µ
⃗j
Vcd = −⃗
µj · EiC (rj ) = − 3 = 3 (9)
4πϵ0 rji 4πϵ0 rij

which gives the same results.

In the case of (II), the D-C interaction becomes

(−zi )zj e2 1 zi zj e2 1
Vdc = + (10)
4πϵ0 |rj − ri | 4πϵ0 |rj − ri − pi |
  " #
zi zj e2  1 1  zi zj e2 1
= − −q =− 1−
4πϵ0 rji 2 − 2r · p + p2
rji 4πϵ0 rji (1 − 2rji · pi /rji
2 + p2 /r 2 )1/2
i ji
ji i i
" #
zi zj e2 1 −2rji · pi 1 p2i 3
≅ − 1−1+ 2 + 2 − 8 (−2rji · pi /rji + pi /rji )
2 2 2 2
. if we assume rji >> pj
4πϵ0 rji 2 rji 2 rji
zi zj e2 rji · pi zi zj e2 pi · rij 1 µ ⃗ i · rij zj e
= 3 =− 3 =− 3 , ⃗ i ≡ zi epi
µ (11)
4πϵ0 rji 4πϵ0 rij 4πϵ0 rij

Please note that C-D and D-C interaction the sign is different. Since the interaction energy is given by zj eφ(|rj − ri |),
the dipoler field is given by

1 µ⃗ i · (r − ri )
φD (r − ri ) = (12)
4πϵ0 |r − ri |3
 3

0 . 4

0 . 2

0 . 2

0 . 4

1 0

5
1 0

1 0
1 0

FIG. 3: dipole field

dipole field
dipole

FIG. 4: dipole-dipole interaction

III. DIPOLE-DIPOLE(D-D) INTERACTION

The dipole-dipole(D-D) interaction can be obtained in the same way. Again we assume rij >> pi , pj .

(−zi )(−zj )e2 1 (−zi )zj e2 1 zi (−zj )e2 1 zi zj e2 1

Vdd = + + + (13)
4πϵ0 |rj − ri | 4πϵ0 |rj + pj − ri | 4πϵ0 |rj − ri − pi | 4πϵ0 |rj + pj − ri − pi |
 
zi zj e2  1 1 1 1 
= −q −q +q
4πϵ0 rji 2 + 2r · p + p2
rji r 2 − 2r · p + p2 r 2 − 2r · p + 2r · p + p2 + p2 − 2p · p
ji j j ji ji i i ji ji i ji j i j i j
"
zi zj e2 1 1
= 1− −
4πϵ0 rji (1 + 2rji · pj /rji2 + p2 /r 2 )1/2
j ji (1 − 2r ji · p i /r 2 2 2 1/2
ji + pi /rji )
#
1
+
(1 − 2rji · pi /rji
2 + 2r · p /r 2 + p2 /r 2 + p2 /r 2 − 2p · p /r 2 )1/2
ji j ji i ij j ji i j ji
"
2
zi zj e2 1 2rji · pj 1 pj 3
= 1−1+ 2 + 2 − 8 (2rji · pj /rji + pj /rji )
2 2 2 2
4πϵ0 rji 2 rji 2 rji
1 −2rji · pi 1 p2i 3
−1 + 2 + 2 − (−2rji · pi /rji
2
+ p2i /rji
2 2
)
2 rji 2 rji 8


1 −2rji · pi 1 2rji · pj 1 p2i 1 p2j 1 2pi · pj 3 −2rji · pi 2rji · pj p2i p2j 2pi · pj 2 

+1 − − − − + + ( + + + − ) 
2 2
rji 2 rji 2 2
2 rji 2
2 rji 2 rji 2 8 2
rji 2
rji 2
rji 2
rji 2
rji 
| {z } | {z }
survive cross term survive
" #
zi zj e2
pi · pj (rji · pi )(rji · pj )
= 2 −3 4
4πϵ0 rji rji rji
" #
1 µi · rij )(rij · µ
(⃗ ⃗j)
Vdd = 3 ⃗i · µ
µ ⃗j − 3 2 (14)
4πϵ0 rij rij
 4

If electric field EiD from i-th dipole can be calculated from φD given above, and the interaction energy can be obtained
by −⃗ µj · EiD (rj ).
µ ¶
∂ ∂ ∂
ED = −∇φD (r − ri ) = − i
i
+j +k φD (r − ri )
∂x ∂y ∂z
1 µix (x − xi ) + µiy (y − yi ) + µiz (z − zi )
φD (r − ri ) =
4πϵ0 [(x − xi )2 + (y − yi )2 + (z − zi )2 ]3/2
1 1 µix i
−∇φD (r − ri )|x = −
4πϵ0 |r − ri |3 [(x − xi )2 + (y − yi )2 + (z − zi )2 ]3/2
1 ⃗ i · (r − ri )
µ −3
− 2(x − xi )i
4πϵ0 [(x − xi )2 + (y − yi )2 + (z − zi )2 ]5/2 2
· ¸
1 ⃗ i · (r − ri )(r − ri )
µ
EiD (r) = − µ⃗ i − 3 (15)
4πϵ0 |r − ri |3 |r − ri |2
" #
1 ⃗ i · (ri − rj )(ri − rj ) · µ
µ ⃗j
Vdd = −⃗ µj · Ed (rj ) =
i
3 ⃗i · µ
µ ⃗j − 3 2 (16)
4πϵ0 rij rij

This equation is the same as the equation given above.

IV. UNIFIED DEFINITION OF C-C, C-D, D-C, AND D-D INTERACTIONS

The total electrostatic potential is given by [check sign→OK]

 

X  X X X 

4πϵ0 Vtot = qi Tij qj −qi T α
µ + µ T α
q − µ T αβ
µ  (17)
| {z } ij j,α i,α ij j i,α ij j,β 
i>j  α α α,β 
C−C | {z }| {z }| {z }
C−D D−C D−D
qi = ezi , µ
⃗ i = (µix , µiy , µiz ) = ezi pi = ezi (pix , piy , piz ) (18)

Here the interaction tensors are given by [check this→OK]

1
Tij = (19)
rij
−3
Tijα = ∇α Tij = −rij,α rij (20)
−5
Tijαβ = ∇α ∇β Tij = (3rij,α rij,β − 2
rij δαβ )rij (21)
−7
Tijαβγ = ∇α ∇β ∇γ Tij = −[15rij,α rij,β rij,γ − 3rij
2
(rij,α δβγ + rij,β δγα + rij,γ δαβ )]rij (22)

Here ∇α means ∂
∂rij,α for α = x, y, z. Tijαβγ will be used in the force formulation.

V. POLARIZATION

When a strong electric field is applied to an atom i, the electrons around atom i starts to deform and a dipole
moment may be induced.
The dipole moment of atom i in the α direction may be written as the superposition of the electric field EjC generated
by the charge of atom j and that EjD by the dipole of atom j

i,α + µi,α ≅ µi,α

µi,α = µstat ind ind
(23)

Usually we take µstatic

i,α = 0. The electric field at atom i can be written as
X
E(ri ) = [EjC (ri ) + EjD (ri )] (24)
j(̸=i)
 5

+ +

d i p o l e

i n d u c e d

FIG. 5: What’s polarization?

( " #)
1 X ri − rj 1 ⃗ ind
µ j · (ri − rj )(ri − rj )
= zj e − ⃗j − 3
µind
(25)
4πϵ0 |ri − rj |3 |ri − rj |3 |ri − rj |2
j(̸=i)
 
1 X X αβ
Eα (ri ) = −Tijα qj + Tij µind
j,β
 (26)
4πϵ0
j(̸=i) β

The induced dipole moment µind

i,α is given by

µind i
i,α = αα,β Eβ (ri ) (27)
i
Here αα,β polarizability tensor of atom i. If we assume
 
αi 0 0
[αi ] =  0 αi 0  (28)
0 0 αi

then, we have

⃗ ind
µ i = αi E(ri ), µind i
i,α = α Eα (ri ) (29)
 
αi X  X αβ

µind
i,α (out) = −Tijα qj + Tij µind
j,β (input) (30)
4πϵ0
j(̸=i) β
 
α i X X
µind
i,x (out) =
−Tijx qj + Tijxβ µind
j,β (input)
 (31)
4πϵ0
j(̸=i) β
 
α i X X
=  xij qj + [
3xij rij,β δxβ
− 3 ]µind (input) (32)
4πϵ0 3
rij 5
rij rij j,β
j(̸=i) β
 
α i X X µind
(input)
=  xij qj + 3xij j,β (input) −
rij,β µind
j,x  (33)
4πϵ0 3
rij 5
rij 3
rij
j(̸=i) β

The last equations should be solved self-consistently.

In the fixed charge model the interaction of C-C is calculated by Ewald method. Then when we consider the induced
dipoles at the atom sites we should C-D, D-C, and D-D interaction. The total C-C, C-D, D-C, D-D interaction is
given by [check this]
 
X X X X
4πϵ0 Vtot = qi Tij qj − qi Tijα µind
j,α + i,α Tij qj −
µind α
µind αβ ind 
i,α Tij µj,β (34)
i>j α α α,β
 6

From Böttcher’s book (Theory off Electric Polarization vol 1 Dielectrics in static field 2nd ed. p110), the energy U
of the induced dipole system

U = −⃗
µind
i · E(ri ) + Upol (35)

where Upol is the work of polarization. At equilibrium, the energy will be minimal with an infinitesimal change of
induced moment

dU = 0, µind
for all d⃗ i (36)

Then we have
⃗ ind
µ 1
dUpol = −d[−⃗
µind
i · E(ri )] = E(ri ) · d⃗
µind
i = i
· d⃗
µind
i = d[(µind 2
i ) ] (37)
αi 2αi
The induced dipole is formed in a reversible process
Z Z µi ind
1 1
Upol = dUpol = d[(µind 2
i ) ]= (µind )2 (38)
2αi 0 2αi i

If we count all the cotribution

X 1
Upol = ⃗ ind · µ
µ
i i
⃗ ind
i (39)
i
2α

The MD code with this polarization scheme is available, e.g. Amber or Lucretius.
 7

FIG. 6: long-range electrostatic interaction

 8

FIG. 7: Ewald sum convergence