Plasmon hybridisation in metal nanostructures

B. Sreeganesh
The incompressible uid model for spherical nanoparticles Plasmons are assumed to be incom-
pressible irrotational deformations of the conduction electron gas of the nanoparticle [3]. The current density
J of the conduction electron gas, can be written in terms of the velocity of the electron gas v and its charge
density as J = v. The velocity can be further written as the gradient of a scalar, v =

. In continuum
mechanics, incompressible ow is mathematically stated as .J = 0. This implies that
2
= 0, which is
the familiar Laplace equation. If the charge density deformations due to some external perturbations are
innitesimally small, it can be assumed to be conned to the surface of the spherical nanoparticle. The
relation between the surface charge density and the scalar can be computed as

t
= n
0
e

n
(1)
where n is the surface normal vector, n
0
is the volume charge density and e is the electric charge. The
dynamics of the deformations of the uid can be obtained from the Lagrangian of the system, which is given
by,
L =
n
0
m
e
2
_

n
0
e
dS
1
2
_
(r)(r

)
|r r

|
dS
r
dS
r
(2)
The solution to the Laplace equation for the scalar , written as a sum of spherical harmonics
(r, ) =

l,m
_
1
lb
2l+1

t
S
lm
(t)r
l
Y
lm
() (3)
where Y
lm
() are the spherical harmonics with angular variables (, ) and S
lm
(t) is a time dependent
parameter, which is the generalised position. The Lagrangian in terms of this generalised position is
L =
n
0
m
e
2
_
_

l,m

t
s
2
l,m

2
s,l
s
2
l,m
_
_
(4)
where
s,l
=
b
_
l
2l + 1
is the frequency of a particular mode as a function of the bulk plasmon frequency

b
=

n
0
e
2

0
m
e
.
Figure 1: Interacting spherical nanoparticles
Plasmon hybridisation in nanoparticle dimers In a nanoparticle dimer, the plasmons of the individual
nanospheres interact with each other electrostatically and solving the Lagrangian for this system gives us
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the various modes of the plasmon vibrations [4]. The Lagrangian for two interacting spheres for a given
azimuthal number m, is given by
L
(m)
=
n
0
m
e
2

i,j
_
_

t
s
2
i

2
s,i
s
2
i
_

i,j


2
b
4
v
(m)
ij
(D)s
i
s
j
_
(5)
where D is the distance between the centers of the nanospheres. v
(m)
ij
is the electrostatic coupling term,
given by
v
(m)
ij
= 4
_
l
i
l
j
R
2li+1
i
_
d
j
sin
j
P
m
li
(cos
i
(
j
))
(2l
i
+ 1) X
i
(
j
)
li+1
P
m
li
(cos
j
) , (6)
where R
i
and R
j
are the radii of the two spheres and P
m
l
(cos()) are the Legendre polynomials. The
Euler-Lagrange equation results in an eigenvalue problem
det
_
A
(m)
ij

2
_
= 0 (7)
where the matrix A is dened by
A
(m)
ij
=
2
i

ij
+

2
b
8
_
v
(m)
ij
+ v
(m)
ji
_
(8)
The solutions of this secular determinant gives the frequencies of vibrations of the collective plasmon modes.
Figure 2: Plasmon energy levels for m = 0 and m = 1 modes
It can be noted from Fig.2 that the coupling of a particular mode between the two nanospheres results
in two collective modes and hence the name hybridisation. Plasmon hybridisation method can be used to
calculate the plasmon modes of nanoparticles with various shapes [1] and structures [2], in which there are
more complex couplings between various modes of the individual nanoparticles.
References
[1] P Nordlander Daniel W Brandl, C Oubre. J. Chem. Phys., 123, 2005.
[2] P Nordlander Daniel W Brandl, Nikolay A Martin. J. Phys. Chem. B, 110:1230212310, 2006.
[3] P Nordlander E Pordan. J. Chem. Phys., 120(5444), 2004.
[4] C Oubre P Nordlander. Nano Lett., 4(5):899903, 2004.
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