J O U R N A L O F M A T E R I A L S S C I E N C E L E T T E R S 2 1, 2 0 0 2, 1743 – 1745

Size effect on the cohesive energy of nanoparticle

W. H. QI, M. P. WANG
Department of Materials Science and Engineering, Central South University, Changsha,
410082, People’s Republic of China
E-mail: qiwh216@mail.csu.edu.cn

Cohesive energy is an important physical quantity to ac- area variation is

count for the strength of metallic bonds, which equals
to the energy to divide the metallic crystal into individ- S = n · πd 2 − π D 2 (4)
ual atoms. The cohesive energy, in other words, is the
heat of sublimation, which can be determined by exper- We exerted energy E n to make the particle changed into
iments [1] or computed by theoretical methods such as n atoms, in other word, the result of exerting E n is to ob-
cellular method [2], density function theory [3], KKR tain the surface area S. Apparently, E n is the cohesive
method [4], linear muffin-tin orbital method [5], etc. energy of n atoms and equals to the surface energy of
All these methods are developed for calculating the co- solid whose surface area is S. Let the surface energy
hesive energy of bulk material. per unit area at 0 K is γ0 , then we have
The most important characteristic of a nanoparticle
is its size effect, i.e., the properties of a nanoparti- E n = S · γ0
cle are different from the corresponding bulk material
[6–9]. However, size effect on the cohesive energies of i.e.,
nanoparticles has not been reported in the literature.
In this letter, a simple method is developed to cal-
E n = π · γ0 · (nd 2 − D 2 ) (5)
culate the cohesive energy of nanoparticle; this method
shows that the cohesive energy of nanoparticle depends
then the cohesive energy per atom is
on its size, i.e., the cohesive energy increases with in-
creasing the particle size. When the particle size is large  
enough, the cohesive energy will approach value of D2
E = π · γ0 d 2 − (6)
the corresponding bulk material. Meanwhile, the cal- n
culated values of bulk metals are in agreement with the
experimental results. Considering Equation 2, we have
According to the definition of cohesive energy, we  
suppose there exists a metallic particle whose diameter d
E = π · γ0 · d 1 −
2
(7)
is D, and is composed of n atoms. The surface area S0 D
of the particle is
For three different structures bcc, fcc and hcp, d can be
S0 = π D 2 (1) determined from the lattice parameters [10]

Assuming that we can separate the particle into n iden-  (3/π)1/3 a bcc

tical spherical atoms (the diameters of the atoms are d) d = (3/2π)1/3 a fcc (8)
without changing its volume by exerting energy E n , we 
 √ 2 1/3
have (3 3a c/2π ) hcp
 3  3 Equation 2 is the formula to calculate the cohesive en-
4 D 4 d
π =n· π ergy of solid in ideal case. However, we must take the
3 2 3 2
difference between real particle (or atoms) and the ideal
sphere into account, so it is necessary to introduce a fac-
i.e.,
tor k to account for the difference. Therefore,
D3  
n= (2)  d
d3 E = k · π · γ0 · d 1 −2
(9)
D
the surface area of n atoms is considering the fact that the sphere has smaller surface
area compared with other forms of equivalent volume,
S = n · π d2 (3) we have k > 1 generally.
The quantity d in Equation 9 denotes the diameter
when the particle is changed into n atoms, the surface of a metal atom, in general, its size is only several
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C 2002 Kluwer Academic Publishers 1743
T A B L E I Calculation values and experiment values of bulk metals

E b (kJ/mol) E b (kJ/mol) [1] E b (kJ/mol) E b (kJ/mol) [1]

Metal (calculation) (experiment) Metal (calculation) (experiment)

V 524 525 Ag 289 284

Ta 732 782 Au 358 368
Mo 642 658 Pb 207 196
Na 105 107 Sc 358 376
K 91.1 90.1 Y 396 422
Rb 82.5 82.2 Ti 485 468
Cs 78.8 77.6 Hf 610 621
Rh 552 554 Tc 629 661
Ni 421 428 Re 766 775
Pt 544 564 Co 443 424
Cu 335 336 Ru 606 650

angstroms. For traditional metals, d/D is about 10−7 .

Of course, this term can be ignored when we calculate
the cohesive energy of bulk materials. We can rewrite
Equation 9 as

E b = k · π · γ0 · d 2 (10)

where E b is the cohesive energy of bulk material. From

this equation, we find that the cohesive energy is lin-
ear function of surface energy per area, which is the
same as the result given by Miedema [11]. According
to Equation 10, we can calculate the cohesive energies
of metal. The calculation result is listed in Table I, the
values of lattice parameters and surface energies of dif-
ferent metal element are selected from references [10]
and [12]. After comparing the calculation values and
experimental results, we find it is safe to choose the
factor k as 1.2 for three different structure bcc, fcc and
hcp. It is apparent that our calculated data agree with
the experimental values.
When the particle is fairly small, i.e., the size of D
is several nanometers or smaller, d/D is about 10−2 to
10−1 . At this moment, the particle size has an effect on
its cohesive energy. This effect cannot be ignored. Con-
sidering equation (10),we can rewrite equation (9) as
 
d than 1% [8] and this is ignored in our calculation.
E p = Eb · 1 −
D
where E p is the cohesive energy of nanoparticle. From
Equation 11, the cohesive energies of metal nanopar-
ticles can be obtained. Taking Cu for example, we can
plot the curve of the cohesive energy as a function of
the particle size, D, (Fig. 1) based on Equation 11.
It is shown that the cohesive energy increases with
increasing the particle size and when the particle size is
larger than 100 nm, the cohesive energy will approach
the constant-bulk value. From this point, we can say
that the boundary of size effect is 100 nm. It is known
that the cohesive energy of metal discloses the strength
of metallic bond. According to our result, decreasing
the cohesive energy of nanoparticle means decreasing
the strength of the corresponding metallic bond. So the
metallic bond will be broken much easier which will
lead to decreasing the melting point of nanoparticle.
In fact, there are experimental results supporting our
prediction [6, 7], i.e., the fact that the melting point of
Figure 1 The cohesive energy of Cu nanoparticles depending on their
size.
nanoparticle will decrease with decreasing the particle
size, is just the quantitive proof of our method.
It is reported that the lattice parameter of metallic
nanoparticle contracts with decreasing their particle
size [8, 9], which means that the lattice parameter will
change a little if the particle size fairly small. However,
for most metal particle, the ratio of contraction is less
(11) In conclusion, a method is proposed in this letter to
calculate the cohesive energy of metal, and the factor
k is determined as 1.2 for bcc, fcc and hcp structures.
On one hand, we can calculate the cohesive energies of
bulk metal materials based on our method, meanwhile,
if the cohesive energy is determined by experiment, the
formula (10) can also be used to calculate the surface
energies of metals. On the other hand, our method can
be used to predict size effect on the cohesive energies
of nanoparticles, which decreases with decreasing the
particle size. For cohensive energy is a very important
quantity, we are confident that the method developed
in this letter will play an important role in theory and
experiment.
References
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3. P . H O H E N B E R G and W . K O H N , Phys. Rev. B 136 (1964) 864.

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Received 25 April
and accepted 7 August 2002
1745