2010 Third International Conference on Information and Computing
The influence about Mg atom inserting on electronic structure and electronic
conductivity of C72 fullerene
Huo Xinxia
School of Science, Jiangnan University,
Wu xi, 214122, P. R. China
e-mail: huoxinxia@sohu.com
AbstractThe first principle based on the density functional
theory (DFT) and nonequilibrium Green's function method is
adopted to analyze the electronic structure and electronic
transmission properties of C72 and Mg@C72 fullerene
molecular bridges between Au(1,1,1) electrodes. The electronic
structure and the electronic transmission probability are
calculated out. The factors affecting the electronic structure
and electronic transmission characteristic are analyzed then. I-
V curves and conductance curves are all calculated out. The
results show metal Mg atom inserting does not improve the
transmission performance of C72 molecule, but reduces the
transmission performance.
Keywords- Mg@C72 molecule, electric structure, electronic
transmission, I-V curves
I. INTRODUCTION
People have interested in studying molecular electric
characteristic since the conductivity of organic molecules
was found in 1972[1]. Fullerene derivatives about metal
atoms and alkali metal atoms, such as M@C60 (M=Na, Ka,
La, Ca)M@C80 (M=Yb, La)M@C82 (M=Yb, La, Ca,
Dy) M@C84 (M=Yb, Y, Sc) M@C88 (M=Ca, La)
M@C36 (M=Mo, Li, Na, K, Mg, Ca, Be) and so on[2-7] have
been studied, the results show that they have many new
electronic messaging function. A large number of research
and experiments show that fullerenes will become one
important part of molecular devices.
Although C72 fullerenes macro-volume synthesis has not
been achieved so far, people have confirmed the existence of
C72 molecule through the experiment of synthesizing M@C72
(M=Ca, La)[8], so that people have interested in C72
molecule. It is significant to study the influence about Mg
atom inserting on electric structure and electric conductance
of C72 because Mg atom and Ca atom belong to the
homologue in the periodic table. People have only studied
the structural characteristics, electronic structure and so on
so far[9-13], but the electronic transmission characteristics
have not been studied. In this paper, two molecular devices
about C72 and Mg@C72 linked to two Au(1,1,1) electrodes
are designed. We study the influence about Mg atom
inserting on electric structure and electronic conductivity of
C72 molecule in this paper, and the results would provide
important theoretical basis for designing and application of
C72 molecular device.
978-0-7695-4047-4/10 $26.00 2010 IEEE
DOI 10.1109/ICIC.2010.110
Wang Liguang
School of Science, Jiangnan University,
Wu xi, 214122, P. R. China
e-mail: wangliguang@jiangnan.edu.cn
II. MODEEL AND METHOD
The model about electronic transmission for Mg@C72
molecule is shown as Fig.1.
Figure 1. The electronic transmission system of Au-Mg@C72-2S-Au
C72 molecule has D6d symmetry and there are two
hexagons symmetrical. We first optimize C72 molecule with
DFT at b3lyp/6-31G(d) and obtain the stable configuration.
Taking into account the interaction between the molecular
devices and the electrodes, we coupled a sulfur(S) atom
respectively to the two symmetry plane first written as C72-
2S, optimize the extended molecule C72-2S and obtain the
stable configuration, then let the Au(1,1,1) electrodes
connect the two sulfur atoms and the transmission system is
obtained written as Au-C72-2S-Au. The process of
embedding Mg atom to C72 molecule is: first, Mg atom is
embedded in the optimized C72 molecule written as
Mg@C72, then Mg@C72 is optimized, the configuration after
optimization also has D6d symmetry and Mg atom is located
in the center of the carbon cage. The design process of
system Au-Mg@C72-2S-Au is same with the design process
of system Au-C72-2S-Au. The contact between the Au
electrodes and the two sulfur atoms is highlighted. Because
the transmission system is added two S atoms which are as
leads and C72 molecule is not connected to Au electrodes
directly, we neednt consider the top site adsorption effect
which Au electrodes are to C72 molecule[14-18]. In
transmission process, electrode current flows from the left
electrode to the right electrode. All calculations about DFT
are achieved with Gaussian package.
In this paper, we adopt the first principle based on DFT
and nonequilibrium Green's function method [19-22].The
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environment temperature about electronic transmission
system is set to 300K. According to Landauer-Bttiker
theory[23], the electronic transmission probability is

TSD ( E ) = Tr[S G R ( E )D G A ( E )] (1)

where E denotes electric energy, S(D) denotes the coupling

between the electrodes and the linked carbon atoms, GR(A)
denotes the retarded or the advanced Greens function of the HOMO(a) LUMO(a)
whole extended molecule. The formulation for calculating
states of density is given by

1
DOS ( E ) = Tr[i (G R G A S ] (2)
2
The formulation about calculating the current when outer
bias voltage is added to electrodes is given by
2e
h
I= dET ( E )[ f ( E , u1 ) f ( E , u 2 )] (1)
where E denotes system energy, T(E) denotes the
transmission coefficient at energy E, e denotes electric
quantity.
III. RESULT AND DISCUSSION
Fig.2 gives the molecular orbital of HOMO, LUMO
calculated by DFT about C72 and Mg@C72 molecules. We
obtain the energy level of HOMO, LUMO and Fermi level
about C72 and Mg@C72 molecules by calculation. HOMO is
-6.287eV, LUMO is -3.658eV, Fermi level is -4.055eV, the
energy gap is 2.628eV about C72 molecule, and the energy
gap is 1.556eV with DFT at b3lyp/3-21G* which is same as
the result in preference [24]. Fermi level locates in the band
gap, so C72 molecule have obvious conductor characteristic
in theory. (a) stands for HOMO and LUMO of C72 molecule.
(b) stands for HOMO and LUMO of Mg@C72 molecule. (a)
shows big molecular orbital are formed and these
orbital just connect the two symmetry planes which connect
the electrodes, thus electronic transmission is likely to occur
in Au-C72-2S-Au, the result is the reason why electrodes are
added to the two planes. (a) also shows electron clouds
concentrate mainly on the molecular shell, the result shows
the electronic transmission occurs mainly on the C72
molecular shell. HOMO is -4.179eV, LUMO is -3.663eV,
Fermi level is -3.997eV, the energy gap is only 0.516eV
about Mg@C72 molecule. There are many new molecular
orbital formed in the shell of C72 molecule because of Mg
inserting, the result leads the energy gap to become smaller.
Although the energy gap is very small, but there are not big
molecular orbital formed, consequently electronic
transmission is more difficult to place in system Au-
Mg@C72-2S-Au. (b) shows the electron clouds mainly
distribute in the shell, so electronic transmission occurs
mainly in the shell.
HOMO(b) LUMO(b)
Figure 2. Molecule orbitl of HOMO and LUMO about C72 and Mg@ C72
molecule
Fig.3 gives transmission spectrum and DOS about
systems Au-C72-2S-Au and Au-Mg@C72-2S-Au. (a) and (b)
represent the transmission spectrum and DOS respectively
about Au-C72-2S-Au, (c) and (d) represent the transmission
spectrum and DOS respectively about Au-Mg@C72-2S-Au.
(a) and (c) show the transmission probability about system
Au-C72-2S-Au is much bigger than Au-Mg@C72-2S-Au at
the average Fermi level 0eV which shows the transmission
performance of Au-C72-2S-Au is better than that of Au-
Mg@C72-2S-Au, this is because Fermi level is where the
probability which electron occur is biggest. The transmission
probability about system Au-C72-2S-Au is much bigger than
that about system Au-Mg@C72-2S-Au at the average Fermi
level 0eV, the reason is that there are many big molecular
orbital formed in C72 molecule and the electron at
molecular orbital are the most active. The number of
transmission probability peaks and DOS peaks about system
Au-Mg@C72-2S-Au is much than that about system Au-C72-
2S-Au which is caused by there being many new molecular
orbital and the energy gap being very small for Mg atom
inserting. (b) and (d) show the peaks of DOS about C72 are
more sharp than those about Mg@C72, the result shows the
resonance phenomenon clearly enhances between incident
electron energy and the energy level of C72 and electronic
transmission is easy to occur.

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 Fig.4 gives the I-V curves and conductance curves about
transmission systems Au-C72-2S-Au and Au-Mg@C72-2S-
Au. (a) stands for the I-V curves about transmission systems
Au-C72-2S-Au and Au-Mg@C72-2S-Au, (b) stands for the
conductance curves about transmission systems Au-C72-2S-
Au and Au-Mg@C72-2S-Au. (a) shows the current through
system Au-C72-2S-Au is much bigger than that through
system Au-Mg@C72-2S-Au when the bias voltage added is
same, and (b) also shows the conductance about system Au-
C72-2S-Au is bigger than that about system Au-Mg@C72-2S-
Au in almost every bias voltage when the bias voltage added
is same, the results show that the transmission performance
of Au-C72-2S-Au is better than that of Au-Mg@C72-2S-Au.
The results are caused by there being big molecular
orbital formed in C72 molecule while there being no
molecular orbital formed in Mg@C72 molecule. The results
also show the transmission performance of transmission
system is not better even the energy gap is very small when
there are not big molecular orbital formed. The results
are consistent with the physical facts. The results as above
show metal Mg atom inserting does not improve the
transmission performance of C72 molecule, but reduces the
transmission performance.

Figure 4. I-V curves and conductance curves about transmission systems

Au-C72-2S-Au and Au-Mg@C72-2S-Au

IV. CONCLUSION
Figure 3. Transmission spectrum and DOS about the system Au-C72-2S-
Au and Au-Mg@C72-2S-Au
In this paper, we have studied electronic structure and
transmission characteristics of C72 and Mg@C72 molecules in

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theory by the first principle based on DFT and [9] Tang Chunmei, Zhu Weihua and Deng Kaiming 2009 J. Mol.
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This paper is Supported by the State Key Development 121: 1113-1114
Program for Basic Research of China (Grant No [14] Tzeng C T and Lo W S 2000 Phys. Rev. B 61: 2263-2272
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