2.

Light in matter: Refractive index of Metal

What is Plasmonics?
• Plasmonics is a relatively new technology in the
optics field, starting in about the year 2000/2001. It is
a way of combing the best parts of both electrical and
optical systems at nanoscale dimensions. Namely the
size of electrics with the speed and frequencies of
optics.
• Just like photonics is the study of photons,
plasmonics is the study of (surface) plasmons.

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• Plasmons travel at the speed of light and are created when light
hits a metal at a particular angle, causing waves to propagate
through electrons near the surface.

• Plasmons are not a physical entity. You can not trap a Plasmon,
or have a single Plasmon sitting in a box. A Plasmon, or
Plasmon wave is simply a density wave of electrons.

• When light interacts with metal, the electric field of the light
causes the free electrons in the metal to adapt to the light's
frequency, creating these density waves of electrons (Plasmons).
In a plasmonic wave, the electrons do not flow along the wire,
like in electricity. They pass the electric field to the next
electron in the chain, and so on along the metal. Like Newton's
cradle pass the force along each ball till the end.

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Plasmonic Wave From Light Source

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Theory of Surface Plasmon Resonance

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Extinction of light by nanosphere

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 Dielectric function of Metal

• Therefore, to calculate the absorption and scattering cross -

section the dielectric function of the particle is required.
• Drude and Lorentz’s free electron models may be used to
calculate the dielectric functions, where electrons and ions were
treated as simple harmonic oscillations, considering only the
contribution of free electrons.
• However, for the noble metals, we have to consider the effect of
interband transitions and free electrons.
• The interband transitions for copper, silver and gold are 3d->4sp,
4d->5sp, and 5d->6sp and free electrons are 4s, 5s and 6s
respectively.
• For alkali metals, such as sodium and potassium which are
unstable in air, the energy of the band gap is large, so the
interband transitions do not affect the dielectric functions in the
visible range.

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Therefore, the dielectric constant of metal is given by the sum of
contribution from the free electron (εf), given by Drude’s free
electron model of metal and a contribution from the interband
transitions (εib). This yields the following expressions for the
dielectric constant.

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Extinction of Nanorod

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 Assignment 1
Analytical Models
• R1=50 select R2 such a way to get the AR(Aspect ratio
1,2,3,4,5) and calculate absorption,scattering,extinction for
nanorod using Mie-Gans Theory.
• Compare the graph and state your observation? If AR
increases SPR peak and strength increases or decreases?

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 FDTD -Lumerical

Video Tutorial:
https://support.lumerical.com/hc/en-us/articles/360045465173-
My-First-Simulation-Introduction-Basic-Workflow

Mannual:
https://support.lumerical.com/hc/en-
us/articles/360033154434-FDTD-product-reference-manual

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Analytical and Numerical Spectrum Comparison
For Au Nanosphere

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Analytical and Numerical Spectrum Comparison as a
Function of Au Nanosphere Radius

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Scattering Cross-section of Different
Morphology Nanoparticle (FDTD)

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FDTD Simulation of Different
Morphology Nanoparticle

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Scattering Cross-sections (per unit
Volume) of Sphere

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 Concept of Plasmon Coupling
Universal Scaling law for NP:

where A is the maximum fractional plasma resonance shift, is the decay constant, d is
the inter - particle separation, D is the diameter of sphere/rod length

The d/D term in Eq.2.16 was replaced by Jiang fang [163] group as ( V gap/V nanorod )1/3,
where Vgap and Vnanorod denotes the volume of the gap region and nanorod respectively.

where c = 3, 5, 7 are for dipole, quadrupole and octupole respectively

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 Excitation Coupling Theory
• The dipole – dipole interactions between two interacting molecules are
generally described in the framework of excitation coupling theory. [168,
169].

• As predicted by excitation theory, excited – state levels of monomer split

into two levels e.g. lower energy level and a higher energy level relative to
the monomer excited state, upon dimerisation.

• In that process it forms two possible arrangements of the transition dipoles

of the dimer, e.g. in - phase or symmetric and out of phase or antisymmetric
(see Figure.2.12).

• The interaction energy (2U) between the molecules could be approximated

by coulombic interaction between the transition dipole moments of the
monomers, the angle and the distance between the transition dipoles 1 and 2.
[170]
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Excitation Coupling Theory

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Excitation Coupling Theory

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Concept of Plasmon Coupling

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Concept of Plasmon Coupling

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 Excitation Coupling Theory
• However, the excitation coupling theory could be used to
elucidate the optical spectra of AuNR dimers.

• For side - by - side AuNR arrangements (J aggregate) when

polarisation direction is along the inter - particle axis,
transverse polarisation, leads to a red – shift and end - by - end
AuNR arrangements (H aggregate), leads to a too small blue –
shift. That’s because, transverse plasmon dipoles are far apart
even when the rods touch each other.

• As a consequence, the optical properties of the AuNR dimers

and their dependence on dimer orientation appear to be
qualitatively steady with the excitation - coupling model.
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Concept of Strong and Weak Plasmon
Coupling

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When particle separation is greater than 0.1 D, where plasmon
ruler governs, we call it weak coupling and when particle
separation is less than 0.1 D, where the plasmon mode
hybridisation occurs (band splitting), we call it strong coupling
(Figure.2.13).
In the weak coupling regime, plasmon coupling obeys an
exponential relationship with the separation, known as the
universal plasmon ruler equation.
In the strong coupling regime, hybridization of the plasmon
energies occurs similar to molecular bonding and anti - bonding
orbitals.

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Plasmon Coupling of 20 nm (radius)
Au Nanosphere dimer

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 Plasmon Coupling of 40 nm
(radius) Au Nanosphere dimer

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Plasmon Coupling of AR 3.8
Au Nanorod dimer

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Plasmon Coupling of AR 4.3
Au Nanorod dimer

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Plasmon Coupling of Au
Nanosphere trimer

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Plasmon Coupling of Au
Nanorod dimer

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Quantum Yield

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Cross–sections calculated via Mie theory compared
with finite difference time domain (FDTD)

Fig. 1. (a) Extinction, absorption and scattering cross–sections calculated via Mie theory compared
with finite difference time domain (FDTD) simulations for 20 nm radius gold nanospheres. (b) Surface
plasmon resonance (SPR) spectrum of nanorods with semi major axis 43 nm and semi minor axis 10
nm calculated using Mie–Gans theory, refractive index 1.33. While gold nanospheres show one SPR
band in the visible region, gold nanorods show two bands: a strong longitudinal band in the near
infrared region corresponding to electron oscillation along the long axis and a weak transverse band,
similar to that of gold nanospheres in the visible region corresponding to electron oscillations along
the short axis. Inset K vector shows the direction of propagation and E vector shows the direction of
electric field considered for FDTD simulation also Transmission Electron Microscopy (TEM) Images
of AuNS (Fig. 1(a)) and AuNR (Fig. 1(b)). 48
FDTD Simulation of 40 nm Radius Au
Nanosphere Dimer

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 FDTD Simulation of 40 nm
Radius Nanosphere Trimer & QY

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Quantum Yield

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 Sample Question
1. What is Plasmonics?
2. What is surface plasmon resonance (SPR)?
3. What parameter are responsible for SPR?
4. Describe effect of size in SPR peak and strength(cross-section) variation.
5. Describe effect of shape in SPR peak and strength(cross-section) variation.
6. What is Mie Theory? What is the significance of it?
7. What is Mie-Gans Theory? What is the significance of it?
8. Distinguish between analytical models and numerical simulation? Why
numerical simulation is needed?
9. Describe the change of scattering cross-section for different morphology
nanoparticle ?
10. Describe excitation plasmon coupling theory?
11. What is strong coupling and weak coupling?
12. Describe the strong and weak coupling for Au Nanosphere dimer, Au
nanorod dimer and Au nanosphere trimer?
13. What is quantum yield? Describe in terms of monomer-dimer and trimer?

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 Assignment 2
FDTD Simulation
Q1.Perform the FDTD Simulation of 20 and 40 nm Radius Au
Nanosphere Dimer. Describe the strong and weak coupling effect.
Q2. Perform the FDTD Simulation of 20 and 40 nm Radius Ag
Nanosphere Dimer. Describe the strong and weak coupling effect.
Q3.Comparison between Ag and Au nanosphere dimer in terms of radius
and separation

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