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Estrada_Graph Theoretic Approaches to Atomic Vibrations in Fullerenes

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# Gr aph Theor et i c Appr oaches

t o At omi c Vi br at i ons i n
Ful l er enes
Department of Mathematics & Statistics,
Department of Physics
Uni ver si t y of St r at hcl y de, Gl asgow
w w w .est r adal ab. or g
“A f ul l er ene, by def i ni t i on, is a closed convex cage molecule
cont aining only hexagonal and pent agonal faces.”
R. E. Smalley
β
m= 1
θ
0 = + Lx x M
 
( ) x x x V
T
  
L
2
θ
=
( 1)
( 2)
β
m= 1
θ
Edge weight : βθ
1
2
3
4
|
|
|
.
|

\
|
− − −
− −
− − −
− −
= − =
3 1 1 1
1 2 1 0
1 1 3 1
1 0 1 2
A D L
( )

= ≡ ∆ x d x P x x x
i i i
 
2 2

= x d x P x x x x
j i j i
 
) (
.
2
exp
2
exp
2
1
|
.
|

\
|
− =
|
.
|

\
|
− =

=
∞ +
∞ −
α α
α
α
µ
βθ
βθ
y dy
y y y d Z
n
T
  
M
n
µ µ µ ≤ ≤ < = 
2 1
0
( 3)
( 4)
( 5)
.
2
2
exp
~
2
2
2

=
=
∞ +
∞ −
=
|
.
|

\
|
− =
n
n
y dy Z
α
α
α α
α
α
βθµ
π
µ
βθ
0
1
= µ
( )
( )
.
~
2 8
2
2
exp
2
exp
~
2
2
2 2
3
2
2
2
2 2
2

∏ ∑

=

= =

=
∞ +
∞ −
=
∞ +
∞ −
× =
× =
|
.
|

\
|
− × |
.
|

\
|
− ≡
n
i
n n
i
n
i
n
i
U
Z
U
y dy y y U dy I
ν
ν
ν
ν α
α
ν
ν
ν
ν
α α
ν α
α
α ν ν ν ν
ν
ν
βθµ
βθµ
π
βθµ
π
µ
βθ
µ
βθ
( 6)
( 7)
,
~
~
2
2
2

=
= = ≡ ∆
n
i i
i i
U
Z
I
x x
ν
ν
ν
βθµ
( ) ( )
ii i
x
+
= ∆ L
βθ
1
2
+
L
( 8)
( 9)
Est rada, E., Hat ano, N. Chem. Phys. Let t . 486 2010, 166.
( )
ij
n
j i
j i
U U
x x
+
=
=
=

L
βθ
βθλ
ν
ν
ν ν
1
2
( 10)
Est rada, E., Hat ano, N. Chem. Phys. Let t . 486 2010, 166.
Est rada, E., Hat ano, N. Chem. Phys. Let t . 486 2010, 166.
Est rada, E., Hat ano, N. Chem. Phys. Let t . 486 2010, 166.
1
2
3
4
2 , 1

( ) ( ) ( )
2 , 1 2 , 2 1 , 1 2 , 1
2
+ + +
− + = Ω L L L
( )

Ω =
G V j
j i i
R
,
( )
∑ ∑∑
= Ω =
i
i
i j
j i
R G Kf
,
2
1
Klein, D. J. , Randić, M. J. Mat h. Chem. 12 ( 1993) 81.
( ) ( )
|
.
|

\
|
− = = ∆
+
n
Kf
R
n
x
i ii i
1
2
L
( ) ( )
|
.
|

\
|
+ + − Ω − = =
+
2
2 1
2
1
n
Kf
R R
n
x x
j i ij ij j i
L
( ) ( )
∑ ∑
∈ =
Ω − + − =
E j i
ij j i
n
i
i i
n R R
n
R k
n
x V
, 1
2
1
2
1

( 11)
( 12)
( 13)
Est rada, E., Hat ano, N. Physica A. 389 2010, 3648.
( ) ( ) | | ( )
2 2 2
2
j i j i j i ij
x x x x x x − = − ∆ + ∆ = Ω
( ) ( )
2
2
2
x n x n Kf
n
i i
i
∆ = ∆ =

=
( ) ( ) ( ) ( ) | |

=
∆ + ∆ = ∆ + ∆ =
n
i
i i i i
x x n x x n R
1
2 2 2 2
( 14)
( 15)
( 16)
Est rada, E., Hat ano, N. Physica A. 389 2010, 3648.
A graph G is said t o have edge expansion ( K, φ) if
( ) { } S v S u U v u E U S ∈ ∈ ⇒ ∈ ⊂ = ∂ , ,
Set of edges connect ing S t o it s
complement
( ) K S V S S S ≤ ⊆ ∀ ≥ ∂ with , φ
S
S
n S S

≤ 2 / :
min φ
S
S
j j
λ λ µ − =
1
∆x
i
( )
2
=
φ
2
i ( )
¸
(
¸
2

+
φ
j
(i)
2
λ
1
− λ
j
j =3
n

.
n
λ λ λ ≥ ≥ ≥ 
2 1
1 ≡ βθ
2 1
λ λ − = ∆
( 17)
Est rada, E. ; Hat ano, N. ; Mat amala, A. R. I n t he book : Mat hemat ics and
Topology of Fullerenes, A. Graovac; O. Ori; F. Cat aldo, Eds. ; Springer, 2010 t o
appear.
Among all graphs with n nodes, those having
good expansion display the smallest topological
displacements for their nodes.
∆x
i
( )
2
=
1
n
φ
2
i ( )
¸
(
¸
2

+
φ
j
(i)
2
λ
1
− λ
j
j =3
n

|
\

|
.
|
i =1
n

=
1
n
1

+
1
λ
1
− λ
j
j =3
n

|
\

|
.
|
.
Est rada, E. ; Hat ano, N. ; Mat amala, A. R. I n t he book : Mat hemat ics and
Topology of Fullerenes, A. Graovac; O. Ori; F. Cat aldo, Eds. ; Springer, 2010 t o
appear.
( ) ( )
2
,
2
1
2 2 2
ˆ
ˆ
s
s
s
s r
rs s r
s
s
x k A x x
m
p
H
∑ ∑ ∑
− − − + =
ω ω
dx
d
i
p
s

ˆ
s
k
|
|
.
|

\
|
− =
+
s s s
p
m
i
m x a
ˆ
2
1
ˆ
ϖ
ϖ

|
|
.
|

\
|
+ =

s s s
p
m
i
m x a
ˆ
2
1
ˆ
ϖ
ϖ

m
ω
ϖ ≡
( 18)
( ) ( )
− + − + − +
+ + − |
.
|

\
|
+ =

|
|
.
|

\
|
+ =
∑ ∑
∑ ∑
s s rs
s r
r r s s
s
s r
s rs r
s
s
s
a a A a a a a
x A x x
m
p
H
ˆ ˆ ˆ ˆ
2 2
1
ˆ ˆ
2 2
ˆ
ˆ
,
,
2
ϖ
ϖ
ω
ω

=
j
j
H H
ˆ ˆ
( 19)
( 20)
( )
( ) 1
ˆ ˆ
2
ˆ ˆ
2 2
1
ˆ ˆ
ˆ ˆ
2 2
1
ˆ ˆ ˆ
2 2
2
+ + + − |
.
|

\
|
+ =
+ − |
.
|

\
|
+ ≡
− + − + − +
− + − +
j j j j j j j
j j j j j j
b b b b b b
b b b b H
λ
ϖ
ϖ
λ
ϖ
ϖ

( )
+ +

=
j
s
j j
a s b
ˆ
ˆ
ϕ ( )
− −

=
j
s
j j
a s b
ˆ
ˆ
ϕ
| | ( ) ( ) | |
( ) ( )
( ) ( ) ,
ˆ
,
ˆ
ˆ
,
ˆ
,
,
jl l
s
j
rs l
s r
j
s r
s l r j j j
s s
s r
a s a r b b
δ ϕ ϕ
δ ϕ ϕ
ϕ ϕ
= =
=
=

+ − + −
Eigenvect ors of H
( 21)
0 0
1 ˆ
s
H
r s r rs
x e x
Z
x x G
β −

. 0 0
ˆ
H
e Z
β −

( ) ( ) ( ) ( )
( ) ( )
( )
( ) ( ) ( )
( )
( )
(
¸
(

¸

+ − ×
(
¸
(

¸

+ − =
× =

|
|
.
|

\
|
+ =
∏ ∑
∏ ∑
∏ ∑

− +

− + − − +
i
j i
j j
j
j
j i
H
j
H
j jl l
l j
j
l l
i
H
j j l
l j
j rs
s r
Z
e b e b s r
Z
b b e b b s r
Z
G
i
j
i
λ
ϖ β
λ
ϖ β
ϕ ϕ
δ ϕ ϕ
ϕ ϕ
β
β
β
1
2
exp 1
2
3
exp
1
0 0 0
ˆ ˆ
0
1
0
ˆ ˆ ˆ ˆ
0
1
ˆ
ˆ
,
ˆ
,
 
( 22)
( 23)
( 24)
( ) ( ) ( ) .
j
e s r C e C G
j
j
j rs rs
βλ
β
ϕ ϕ

= =
A
( ) ( )

= = ≡
j
j
e e tr G EE Z
βλ
βA
( ) | |

= ∆
j
j r
j
e r x
βλ
ϕ
2
( 25)
( 26)
( 27)
Est rada, E., Rodriguez-Velazquez, A. Phys. Rev. E 71 2005, 056103.
Est rada, E., Hat ano, N. Phys. Rev. E 77 2008, 036111.
Est rada, E., Hat ano, N. Chem. Phys. Let t 439 2007, 247.
1 ≡ ϖ  A H − =
A
A
B
C
B
C
P Q
Q
P
A cl assi cal mechani cs appr oach t o vi br at i ons i n mol ecul es
can be f or mul at ed on t he basi s of t he gener al i sed
Moor e- Penr ose i nver se of t he gr aph Lapl aci an.
A quant um mechani cs appr oach t o vi br at i ons i n mol ecul es
based on coupl ed har moni c osci l l at or s can be f or mul at ed
on t he basi s of t he ex ponent i al adj acency mat r i x of t he gr aph
r epr esent i ng t he mol ecul ar sy st em.
Bot h appr oaches gi ve i mpor t ant i nf or mat i on about t he
ener get i c and st abi l i t y of f ul l er ene i somer s, as w el l as
pr ovi de a t heor et i cal f r amew or k f or empi r i cal obser vat i ons
such as t he ‘ i sol at ed pent agon r ul e’ .
NAOMI CHI HATANO
Institute of Industrial Sciences
University of Tokyo
Japan
Department of Chemistry
University of Concepcion
Chile
PATRI CK W. FOWLER
Department of Chemistry
University of Sheffield
U.K.

“A fullerene, by definition, is a closed convex cage molecule containing only hexagonal and pentagonal faces.” R. E. Smalley

β

θ

m=1

M + Lx = 0 x
 θ T  V ( x ) = x Lx 2

(1) (2)

β 4 θ 1 3 2 m=1 Edge weight: βθ  2 − 1 0 − 1  − 1 3 − 1 − 1 L =D−A = 0 − 1 2 − 1  − 1 − 1 − 1 3   .

∆xi ≡ xi 2   = ∫ xi P(x )dx 2 (3) (4) xi x j   = ∫ xi x j P( x )dx   βθ  T   Z = ∫ dy exp − y My   2  n +∞  βθ  = ∏ ∫ dyα exp − µα yα 2 . −∞  2  α =1 (5) 0 = µ1 < µ 2 ≤  ≤ µ n .

µ1 = 0 n +∞ ~  βθ  Z = ∏ ∫ dyα exp − µ α yα 2  −∞  2  α =2 =∏ α =2 n 2π (6) βθµ α . n n +∞ +∞ ~  βθ  βθ  2 2 I i ≡ ∑ ∫ dyν (U iν yν ) exp − µν yν  × ∏ ∫ dyα exp − µ α yα 2  −∞  2  α = 2 −∞  2  ν =2 α ≠ν U = ∑ iν ν =2 2 n 2 (βθµν )3 2 8π ×∏ α =2 α ≠ν n 2π βθµν ~ n U iν = Z ×∑ . ν =2 βθµν (7) .

486 2010. . Lett. 166. Chem. ν (8) (∆xi ) L+ 2 = (L ) βθ 1 + ii (9) Estrada. E.∆xi ≡ xi 2 = ~ Ii ~ = Z ∑ βθµ ν =2 n U iν 2 .. Hatano. Phys. N.

486 2010. Chem. 166. Hatano. Phys. Lett.xi x j = ∑ ν =2 n U iν U jν βθλν + ij = (L ) βθ 1 (10) Estrada. . E.. N.

Hatano. Phys. 486 2010.. Lett. .Estrada. Chem. 166. E. N.

Hatano.Estrada. 486 2010. E. Chem. .. Phys. Lett. N. 166.

4 1 Ω1. D. M. Math. j = ∑ Ri 2 i j i j∈V G Ri = ∑Ω ( ) i. J. 2 ( ) 1. Randić.J. 2 2 3 Ω1. 12 (1993) 81. 2 Kf (G ) = 1 ∑∑ Ωi. . 2 = L+ ( ) + (L ) + 1. j Klein.1 − 2 L+ 2. Chem. .

. 3648. j∈ ( ) (13) Estrada. . Physica A. E. 389 2010. Hatano.(∆xi ) 2 = L ( ) + ii 1 Kf  =  Ri −  n n  (11) xi x j = L ( ) + ij 1 1 2 Kf  = −  Ω ij − Ri + R j + 2  2 n n  ( ) (12)  1 n 1 V (x ) = ∑ k i Ri − ∑E Ri + R j − nΩ ij 2n i =1 2n i . N.

Physica A.Ω ij = (∆xi ) + ∆x j 2 [ ( ) −2 x x 2 i j ] = (x − x ) i j 2 (14) Ri = n(∆xi ) + ∑ (∆xi ) = n (∆xi ) + (∆x ) 2 2 2 i =1 n [ 2 ] (15) Kf = n∑ (∆xi ) = n 2 (∆x ) n 2 i =i 2 (16) Estrada.. 3648. . Hatano. 389 2010. E. N.

S S ∂S = { ⊂ E (u . ∀S ⊆ V with S ≤ K ∂S S S: S ≤n / 2 φ ≡ min . φ) if ∂ (S ) ≥ φ S . v ∈ S } U Set of edges connecting S to its complement A graph G is said to have edge expansion (K. v ) ∈ U ⇒ u ∈ S .

Cataldo. Ori. R. 2010 to appear. O. F. Hatano. N. A.. In the book: Mathematics and Topology of Fullerenes. . Springer.. ∆ j = 3 λ1 − λ j 2 (17) Estrada.. Graovac. Eds. E. Matamala.µ j = λ1 − λ j λ1 ≥ λ2 ≥  ≥ λn βθ ≡ 1 ∆ = λ1 − λ 2 (∆xi ) 2 n φ (i )2 φ2 (i )  j = +∑ . A.

Hatano. R.(∆xi ) 2 n n φ (i )2   φ2 (i ) 2 1 1 1  1 j   + = ∑ ∑λ −λ  = n ∆ +∑λ −λ . In the book: Mathematics and Topology of Fullerenes. Estrada. Cataldo. A. . Springer. 2010 to appear. A. F. Matamala. Ori. E. Graovac. O.. ∆ n i =1   j=3 1 j=3 1 j j n Among all graphs with n nodes.. N. Eds. those having good expansion display the smallest topological displacements for their nodes..

.

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s 2 s 2 (18) ˆ ps ≡  d i dx ks ˆ a s+ =  1  i ˆ  x s mϖ − ps   2  mϖ   ϖ ≡ ω m ˆ a s− =  1  i ˆ  x s mϖ + ps   2  mϖ   .ˆ ps ω ˆ = (xr − x s )2 Ars −∑ ω (k s − 1)x s2 H ∑ +∑ s 2m r .

s  s ( ) ( ) (19) ˆ ˆ H = ∑H j j (20) .s  1  ϖ  ˆ ˆ ˆ ˆ ˆ ˆ = ∑ ϖ  as+ as− +  − ∑ ar+ + ar− Ars as+ + as− 2  2 r .ˆ ˆ =  ps + ω x 2  − ω x A x H ∑  ∑ r rs s s  2  s  2m r .

s Eigenvectors of H . ϕ s r .ϕ (s )aˆ ] − j + j j − r l + s = ∑ ϕ j (r ) l (s )δ rs ϕ = ∑ ϕ j (s ) l (s ) = δ jl . bˆ ] = ∑ [ϕ (r )aˆ .s r .ˆ ˆ ˆ ≡ ϖ  b + b − + 1  − ϖ λ b + + b − 2 Hj  ˆj ˆj  j j j 2 2   ˆ + ˆ − 1  ϖ ˆ + 2 + b − 2 + 2b + b − + 1 ˆ ˆ ˆ λ j bj = ϖ  b j b j +  − j j j 2 2  ( ) ( ) (21) ˆ ˆj b + = ∑ ϕ j (s )a + j s ˆ ˆj b − = ∑ ϕ j (s )a − j s [bˆ .

Grs = = = 1 Z 1 Z 1 Z ˆ  ˆ ˆ  ˆ ˆ ϕ j (r ) l (s ) 0 b + + b −  ∏ e − βH  bl+ − bl− 0 ϕ ∑ j j   i ( ) j .Grs x r x s 1 ˆ − βH 0 xr e xs 0 ≡ Z ˆ − βH (22) (23) Z ≡ 0e 0.l  i  ( ) ˆ ∑ ϕ j (r )ϕl (s )δ jl 0 b −e j j .l ˆ − βH j ˆ ˆ b + 0 × ∏ 0 e − βH i 0 j i (≠ j ) (24) i ∑ ϕ j (r )ϕ j (s )exp− j  3 β ϖ 1+ λ j 2  ( ) × ∏ exp− βϖ (1 + λ )    2  i (≠ j )   .

056103. N. . Estrada. E. E. E 77 2008. 247. 036111.. Rev. Phys. A. Hatano. Rev. E. (25) Z ≡ EE (G ) = tr e ( )= ∑e βA j βλ j (26) (27) ∆xr = ∑ ϕ j (r ) e 2 j [ ] βλ j Estrada. N.ϖ ≡ 1 H = −A Grs = C e βA ( ) rs = C ∑ ϕ j (r ) j (s )e ϕ j βλ j . Rodriguez-Velazquez. Phys.. Lett 439 2007. Estrada. Chem.. Hatano. E 71 2005. Phys.

.

.

.

.

B C A B A C .

P Q Q P .

.

.

.

A quantum mechanics approach to vibrations in molecules based on coupled harmonic oscillators can be formulated on the basis of the exponential adjacency matrix of the graph representing the molecular system. Both approaches give important information about the energetic and stability of fullerene isomers. as well as provide a theoretical framework for empirical observations such as the ‘isolated pentagon rule’.A classical mechanics approach to vibrations in molecules can be formulated on the basis of the generalised Moore-Penrose inverse of the graph Laplacian. .

MATAMALA Department of Chemistry University of Concepcion Chile PATRICK W. .K.NAOMICHI HATANO Institute of Industrial Sciences University of Tokyo Japan ADELIO R. FOWLER Department of Chemistry University of Sheffield U.

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