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Appendix B  ZGNR Optical Matrix Elements

B.1  Bloch Wave Functions Prefactors

To obtain CA and CB in Eq. 18, one can substitute Eq. 6 and Eq. 19 into the Shrödinger equation H|ψ⟩=E|ψ⟩. Considering an A-type carbon atom at some atomic site n, and its three nearest neighbors, the Hamiltonian can be written as:

H  = t | BN−n+1⟩ ⟨ An |  + t | BN−n+1′⟩ ⟨ An |  + t | BN−n⟩ ⟨ An |.     (1)

Using Eq. 1 along with the wave functions obtained in Eq. 12, one obtains:

ECA ei kx xnAsin(n θ) =  tCBei kx xN−n+1Bsin((N−n+1)θ) 
 +tCBei kx xN−n+1B′sin((N−n+1)θ) 
 +tCBei kx xN−nBsin((N−n)θ).
    (2)

Therefore, the relation between CA and CB can be written as:

ECAsin(nθ)
=tCB⎡
⎢
⎣
⎛
⎜
⎝
e
ikx⎛
⎝
xN−n+1B−xnA⎞
⎠
 
+e
i kx⎛
⎝
xN−n+1B′−xnA⎞
⎠
 
⎞
⎟
⎠
 
  sin⎛
⎝
(N−n+1)θ⎞
⎠
+e
ikx⎛
⎝
xN−nB−xnA⎞
⎠
 
sin⎛
⎝
(N−n)θ⎞
⎠
e
⎛
⎝
xB′⎞
⎠
 
⎤
⎥
⎦
 
= tCB⎡
⎢
⎢
⎣
2 cos⎛
⎜
⎜
⎝
√
3
2
kx acc⎞
⎟
⎟
⎠
sin((N−n+1)θ)+sin((N−n)θ)⎤
⎥
⎥
⎦
.
    (3)

By employing the relation sin(x)sin(y)=(1/2)[cos(x−y)−cos(x+y)] and using Eq. 22,

ECA = −tCB
sin(θ)
sin((N+1)θ)
.     (4)

Analogously, for the N−n+1th B-type carbon atom one can obtain the following relation:

ECB sin⎛
⎝
⎛
⎝
N−n+1⎞
⎠
θ⎞
⎠
= tCA ⎡
⎢
⎢
⎣
2 cos⎛
⎜
⎜
⎝
√
3
2
 kx acc⎞
⎟
⎟
⎠
sin(nθ) + sin((n−1)θ)⎤
⎥
⎥
⎦
    (5)

which gives

ECB = −tCA
sin(θ)
sin((N+1)θ)
.     (6)

From Eq. 4 and Eq. 6, one can find that CA=± CB.
Also, the dispersion relation can be found by multiplying Eq. 3 by Eq. 5,

E2CACB sin(nθ)sin((N−n+1)θ) 
 
= t2CACB⎡
⎢
⎢
⎢
⎣
4cos2⎛
⎜
⎜
⎝
√
3
2
 kx acc⎞
⎟
⎟
⎠
sin((N−n+1)θ)sin(nθ) 
 
   +2cos⎛
⎜
⎜
⎝
√
3
2
 kx acc⎞
⎟
⎟
⎠
sin((N−n+1)θ)sin((n−1)θ) 
 
   +2cos⎛
⎜
⎜
⎝
√
3
2
 kx acc⎞
⎟
⎟
⎠
sin((N−n)θ) sin(nθ) 
 
   +sin((N−n)θ) sin((n−1)θ)⎤
⎥
⎥
⎥
⎦
.
    (7)

With the help of trigonometric identities and Eq. 22, this expression can be reformatted as

E = ± t ⎡
⎢
⎢
⎣
1+4cos2⎛
⎜
⎜
⎝
√
3
2
 kx acc⎞
⎟
⎟
⎠
+4cos⎛
⎜
⎜
⎝
√
3
2
 kx acc⎞
⎟
⎟
⎠
cos⎛
⎝
θ⎞
⎠
⎤
⎥
⎥
⎦
1/2



 
.     (8)

B.2  Transverse Wave Functions Amplitude

To solve the recursive formula,

φn+1−C φn+φn−1=0,     (9)

one can consider the ansatz φn=tn and follow similar equation,

t2−Ct+1=0.     (10)

This equation is the generating polynomial of the recursive formula 9.
The roots of 10 are

t1,2=
⎛
⎜
⎝
C±√
C2−4
 ⎞
⎟
⎠
2
.     (11)

The general solution of the difference equation is

φn=α t1n+β t2n,     (12)

since t1 is a root of the equation, the other root t2 can be written as: t2=t1−1.
By substituting those two roots in 12 one obtains

φn=α t1n+β t1−n.     (13)

Imposing the initial condition φ0=0 results in

α+β =0,  α =−β,     (14)

and from the 13,

φn=α(t1n−t1−n).     (15)

We obtain

α=
φ1
√
C2−4
,   β=−
φ1
√
C2−4
.     (16)

By substituting 11 and 16 in 15, one obtains

φn=
φ1
√
C2−4
⎛
⎜
⎜
⎝
C+√
C2−4
2
⎞
⎟
⎟
⎠
n



 
−
φ1
√
C2−4
⎛
⎜
⎜
⎝
C−√
C2−4
2
⎞
⎟
⎟
⎠
n



 
.     (17)

17 can be rewritten as

φn=
⎛
⎜
⎜
⎝
C+√
C2−4
2
⎞
⎟
⎟
⎠
 n



 
−⎛
⎜
⎜
⎝
C−√
C2−4
2
⎞
⎟
⎟
⎠
 n



 
√
 C2−4
φ1.     (18)

B.3  Optical Matrix Elements

Using Eq. 12 and Eq. 13 the matrix elements pθ,θ′(kx) ≡ ⟨ +, θ, kx| px | −, θ′, kx⟩ for an interband transition from a valence band state | −, θ, kx⟩ to a conduction band state | +, θ′, kx⟩ are obtained as

Pθ,θ′=(xθ′−xθ)
im0
ℏ
⟨ θ | H | θ′ ⟩     (19)
Pθ,θ′= 
im0
ℏ Ω
 
N
∑
n=1
 
N
∑
m=1
 ⎡
⎢
⎢
⎢
⎣
 
ei k (xmB − xnA) sin(nθ) sin(m θ ′) ⟨ An | H | Bm ⟩ (xmB − xnA)   
 
− ei k (xmA − xnB) sin(nθ ′) sin(mθ) ⟨ Bn | H | Am ⟩ (xmA − xnB) ⎤
⎥
⎥
⎥
⎦
. 
    (20)

Considering only the nearest neighbors, each atom with some index n has two neighbors with index N−n+1 and one neighbor with index N−n, see Fig. 4.1. Therefore, the index m has only three values with ⟨ An | H | Bm ⟩ = t. So we have

 Pθ,θ′=
⎛
⎜
⎜
⎝
i m0
ℏΩ
⎞
⎟
⎟
⎠
⎛
⎜
⎜
⎝
i√
3
acct
2
⎞
⎟
⎟
⎠
N
∑
n=1
⎡
⎢
⎢
⎢
⎣
⎛
⎜
⎝
e
i √
3
kx a/2
 
−e
−i √
3
kx a/2
 
⎞
⎟
⎠
sin(nθ) sin((N−n+1) θ ′) 
 
−⎛
⎜
⎝
e
−i √
3
kx a/2
 
−e
i √
3
kx a/2
 
⎞
⎟
⎠
sin(nθ ′) sin((N−n+1)θ)⎤
⎥
⎥
⎥
⎦
, 
    (21)

after some algebra and replacing Ω from Eq. 16, the optical matrix elements are

Pθ,θ′=
−2√
3
m0 acc t
ℏ (2N+1)
 sin⎛
⎜
⎜
⎝
√
3
2
kacc⎞
⎟
⎟
⎠
N
∑
n=1
⎡
⎢
⎢
⎢
⎣
sin(nθ)sin((N−n+1) θ ′)−
sin(nθ ′)sin((N−n+1)θ)⎤
⎥
⎥
⎥
⎦
.
    (22)

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