Avoided crossing behavior visualized in strongly coupled nanorod dimers

Fan-Cheng Lin(), Jer-Shing Huang()

E-mail : fc.lin25@gmail.com

Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan. ()

Abstract
Upon excitation gold nanorods exhibit localized surface plasmon resonance. The resonance wavelength of longitudinal modes scales with aspect ratio of the nanorods. When two rods are aligned headto-head, the longitudinal modes on each rod couple via the near field in the subwavelength gap. Such strong coupling results in two hybrid modes with different modal profiles and separated with an asymmetric energy splitting. Depending on the symmetry and frequency of the excitation, hybrid modes can be selectively excited. Therefore, nanorod dimers may function as nanoantennas with enhanced field in the gap or as high-Q plasmonic cavities depending on the coupling between two rods. Here, we theoretically investigate the coupling of longitudinal plamonic modes in asymmetric nanorod dimers. Gradually tuning the length of one rod and keeping the other, we have observed coupling behavior similar to adiabatic avoided curve crossing. The asymmetry of energy splitting is found to be different for dipole-dipole coupling and dipole-quadrupole coupling. Since the dark quadrupolar modes radiate less efficient than the dipolar modes, the far-field scattering spectrum may exhibit dip in contrast to peak. This makes it possible to engineer the resonance spectrum of nanorod dimers simply by linking rods with desired length. The result is insightful and provides a guideline for plasmonic enhanced spectrum engineering.

Nanorod dimers Bright-Dark mode splitting

(a)
550

D
B A

2R

L2

L1

L2 = 200 300 (10 point) , L1 = 100 , D = 10 & 30, R = 20 (nm)

(b)
200 210 220 230 240 250 260 270 280 290 300

550

B
L2 L1 D = 10 nm D = 30 nm

Coupling of various L2 with single L1

(a) The dark mode of various L2 couples to single bright mode of fixed L1. The D is 10 nm, and the blue dash line is relative to blue hollow square in (b). (This is extinction spectrum. You also can get the same result from near field.) (b) We get those point from extinction spectrum with change of D. The purple solid circle indicates the fixed bright mode of L1, the black solid square indicates the various dark mode of L2. The antibonding must be excited asymmetric . In this case, although we use the plane wave to forward illuminate. But we also can get the antibonding mode. There is a well-known excited mechanism. Mechanism : The source only excited bright mode(Rod A)(1st bright mode), and the bright mode just like dipole source. The Rod A can excite Rod B (This is asymmetrical excitation). So we can got the antibonding mode.

Frequency (THz)

Frequency (THz)

500

500

450

450

400

400

10

200

220

240

260

280

300

Normalized intensity

Length of L2

(c)

(d)

Electron field distribution antibonding

500

Frequency (THz)

450

Feedgap = 30nm Feedgap = 10nm

Normalized

bonding

Energy level splitting (c) The color in figure (c) and (d) represent the same things in figure (b). All of which are extinction spectrum in addition to long rod(black dash line). (d) This is the
energy splitting of different gap length. In antibonding mode, we can see small intensity in the gap(black hollow square). On the contrary, there is stronger intensity in bonding mode (orange hollow square)

Single rod
z

y y x L 2R

In x-y plane 2R L x
1st bright mode

Current flow of antibonding and bonding mode

Gap = 10 nm A = 100 nm Bright Bright B = 100 nm Diameter = 40 nm A B A Bright Dark B Gap A B Diameter = 40 nm

J i( material 0 ) E

(c)
2nd
16 14

bright mode

1st dark mode

12

(a)
Asymmetrical excitation
Normalized
1.0

10

1st bright mode

Normalized intensity

2nd

bright mode

0.8

0.6

k E

0.4

1st dark mode

0.2

2
0.0

600

800

1000

1200
0 500 600

Wavelength (nm)

640

700

800

900

50 nm 60 nm 70 nm 80 nm 90 nm 100 nm 110 nm 120 nm 130 nm 140 nm 150 nm 160 nm 170 nm 180 nm 190 nm 200 nm 210 nm 220 nm 230 nm 240 nm 250 nm 260 nm 270 nm 280 nm 290 nm 300 nm

D material E ( 0 plasma ) E 0 E plasma E = 10 nm = 100 nm iJ = 250 nm D0

material r 0
n r r , r 1

material n 2 0

30

30

y position (nm)

y position (nm)

Z=0

Antibonding mode
1
-100 -50 0 50 100

-30

-30

-200

-100

100

Wavelength (nm)

L
30

x position (nm)
30 30

x position (nm)
30

(d)
1

y position (nm)

y position (nm)

y position (nm)

y position (nm)

1st dark mode

Wavelength (nm)

(b)
symmetrical excitation
Normalized
1.0 0.8

900

800

1st bright mode

0

-30

0.6

700

40

80

-30

-30 0 40 80

100

200

-30

40

80

x position (nm)
30

x position (nm)

x position (nm)
30

x position (nm)

0.4

0.2

600

640 nm

y position (nm)

0.0 600 800 1000 1200

50

100

150

200

250

300

Wavelength (nm)

Length of L (nm)

-1
0

y position (nm)

Dark mode & bright mode (a) While an asymmetrical excitation The ways of excitation The source of near field spectrum is a Gaussian wave. (a) Dark mode is
excited by asymmetrical illumination. There are three mode can be induced. (Asymmetrical excitation illuminates one side of structure.) (b) Symmetrical excitation must illuminate on the middle of structure or use the forward plane wave. There are only two mode can be induced. on various L of nanorods, we can find more modes with the different L. The red square is which we choose to couple bright mode and dark mode at wavelength of 640 nm. (b) Plot the peaks of 1st bright mode and 1st dark mode peak of various L. The screenshots are electron field distribution from FDTD simulation. We can observe simply that there are stronger field in two place of structure and three place of 1st bright mode and 1st dark

-30

-100

-50

50

100

Bonding mode

-30

-200

-100

100

x position (nm)

x position (nm)

Current density of antibonding and bonding mode The color chart is Jx value(xdirection current density) of x-y plane which get from middle of structure. The arrow chart is Jxy value
( Jxy Jx 2 Jy 2, we also calculate the angle. ) (Note : Current flow is positive charge to negative charge.) In the left side, the current flow of antibonding mode on both sides of the gap are opposite. The right side of the graph can also get the same results.

Nanorod dimers Bright-Bright mode splitting

(a)
560

D B L2 A L1 2R

Frequency (THz)

Frequency (THz)

480

50 60 70 80 90 100 110 120 130 140 150

(b)
560
L2 L1 D = 10 nm D = 30 nm

L1 = 50 150 (11 point) , L2 = 100 , D = 10 & 30, R = 20 (nm)

Change surrounding index

500

THz

500

Coupling of various L1 with single L2

(a) The near field spectrum is energy level splitting when we change L1. (b) The brown solid square is about bright mode of rod B, and the blue solid circle is bright mode of rod A. When L2 is equal to L1, we cant get the peak(antibonding) of green circle from the monitor(black cross) (button screenshot). The antibonding must be excited by asymmetrical excitation(top screenshot). We also change the gap(D) of two rod, the splitting of D = 30nm is smaller than D = 10nm. We can find avoid cross behavior in the table.

400

480

300

n = 1.0 n = 1.1 n = 1.2 n = 1.3 n = 1.4 n = 1.5 n = 1.6 n = 1.7 n = 1.8 n = 1.9 n = 2.0

400

500

Frequency (THz)

Frequency (THz)

bonding mode antibonding mode

300

Surrounding
200

Equation Adj. R-Square antibonding mode antibonding mode

y = a + b*x 0.99267 Intercept Slope Value Standard Error 693.66532 8.37531 -201.1019 5.46345

400

1.0

1.2

1.4

1.6

Index

Bright Bright mode

300

400

400

200

200

1.0

1.2

1.4

1.6

1.8

2.0

Normalized intensity

Surrounding index (n)

When we change the surrounding index, the energy level different between antibonding and bonding is not change a lot. Therefore, we calculate only frequency shift per 1 index of antibonding mode. 201.1(THz)/index
500

50

100

150

Frequency (THz)

THz

Normalized intensity

Length of L2

500

Frequency (THz)

n = 1.0 n = 1.1 n = 1.2 n = 1.3 n = 1.4 n = 1.5

500

bonding mode antibonding mode

400
Equation y = a + b*x Adj. R-Square 0.99776

Surrounding
400

300

antibonding antibonding

Intercept Slope

Value Standard Error 731.8367 6.38194 -238.8899 5.05856

(c)
500

(d)
Antibonding mode

Electron field distribution

1

400

1.0

1.1

1.2
Index

1.3

1.4

Bright Dark mode

300

300 0 1 2 3 4 5

1.0

1.1

1.2

1.3

1.4

1.5

Normalized intensity
Frequency (THz)

Surrounding index (n)

When we change the surrounding index, the energy level different between antibonding and bonding is not also change a lot. Therefore, we calculate only frequency shift per 1 index of antibonding mode. 238.9 (THz)/index

450

Feedgap = 30nm
400

Result
A B
length of B length of A gap = 10 nm gap = 10 nm

Feedgap = 10nm Bonding mode

0.0 0.2 0.4 0.6 0.8 1.0

Normalized

500

Bright mode Dark mode

400

Energy level splitting (c) This is near field spectrum when R = 20 nm, L2 = L1 = 100 nm. Blue line is the background of
coupling. (When two rods far away, just like single rod) The black one and red one are the spectrum of D = 10 nm and 30 nm, respectively. (d) This is the energy splitting of different gap length. The antibonding mode is negative to negative(or positive to positive), so the electron field intensity is smaller in the gap.( black hollow square) On the contrary, the bonding mode is negative to positive, so that the electron field intensity is stronger than antibonding mode.

Bright mode
100 200 300

1. Dark mode is only induced by asymmetrical illumination. 2. The more smaller length of feedgap, the more stronger energy splitting. 3. When the modes of two gold rods at the same energy level, antibonding mode can only be asymmetrical exposure to stimulate 4. When the energy level in two rods are more close, we can observe clearly the phenomenon of avoided crossing behavior.

Frequency (THz)

Length of rod B (nm)

0
1.8 2.0 1.5

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4