Clusters of Ge and O Atoms and the Raman Spectra of

Vitreous GeO
2

Ahmad Nazrul Rosli
*
, Noriza Ahmad Zabidi
*
, Christopher G. J esudason

, Hasan
Abu Kassim
*
and Keshav N. Shrivastava
*

*Department of Physics, Faculty of Science, University of Malaya, Kuala Lumpur, 50603 Malaysia.

Department of Chemistry, Faculty of Science, University of Malaya, Kuala Lumpur, 50603 Malaysia
Abstract. We have constructed the clusters of atoms of germanium and oxygen atoms by using the density-functional
theory. By optimizing the structures for the minimum energy of the Kohn-Sham equation, we are able to calculate the
bond lengths. We use the local density approximation to obtain the electronic binding energy for each cluster. We find
the vibrational frequencies of each and every cluster and compare the calculated values with those measured from the
Raman spectra of GeO
2
glass. The glass involves clustering of atoms. Hence some of the calculated values match with
those found in the experimental data. In this way, we find that Ge-O
2
(triangular), Ge-O
3
(pyramidal) and Ge-O
6

(pyramidal) clusters are present in the glassy state.
Keywords: Vibrational frequencies, density-functional theory, glass.
PACS: 33.20.Fb, 63.50.Lm
INTRODUCTION
The phenomenon of self-organization is often
found in the glassy state. The clusters of atoms form a
network which self-organizes the orientations and
geometrical coordinates. In some of the glassy states,
the self-organization goes on for a long time and it is
characterized by long-relaxation times [1,2]. The
contact between the atomic levels and the lattice is
much less in the glassy state than in a crystalline state
so that the atoms take a long time to come to a thermal
equilibrium. Our own effort [3-11] shows that there
are clusters of atoms of varying sizes and shapes
which have to adjust their orientation with respect to
their neighbours. Since, the neighbouring clusters are
not of the same size as that of the previous clusters, it
takes a long time to find the equilibrium coordinates. It
has been pointed out that there is considerable rigidity
and flexibility in the electrolyte glasses [12], and there
are phase transitions in the rigidity of the glassy state
[13].
The Raman spectra of GeO
2
in vitreous form were
recorded by Galeener and Lucovsky [14]. There is a
clear difference between a crystalline material and a
vitreous material and there is a network glassy state
which is distinguished from the crystalline state. In the
crystalline state, the usual longitudinal optic (LO) and
the transverse optic (TO) modes are often found,
Galeener and Lucovsky claim to have found 347 cm
-1

(sharp)(LO), 973 cm
-1
(broad)(LO), 278 cm
-1
(TO),
857 cm
-1
(TO), 595 cm
-1
(LO) and 556 cm
-1
(TO)
modes in GeO
2
. Subsequent work by Galeener et al.
[15] found that there are acoustic, rocking and band
regions in the Raman spectra. The observation of low
frequency bands is assigned to bosons [16,17]. The
effect of disorder on the Raman scattering in Ge-Ga-S
glass allows all possible modes [18]. A neat study of
the Raman spectra of the glassy state GeO
2
gives the
bands at 344, 419 (strong), 520, 556, 595, 857 and 973
cm
-1
. The bands at 556 and 595 cm
-1
are affected by
quenching the samples [19].
In this paper, we report the calculation of
vibrational frequencies of several clusters of atoms of
Ge and oxygen. From these calculations we identify
that OO mode in GeO
2
is present. Similarly, we are
able to show that, GeO
3
(pyramidal) clusters are
present in the glassy state. We have performed the
calculation by using the density-functional theory of
Kohn and Sham [20] and have compared the
calculated values with those measured from the Raman
spectra [19]. Our method of calculation uses the
density-functional theory in the local-density
approximation (LDA). We have used the programme
called DMol
3
kindly provided by Accelrys software,
Inc. of San Diego, California. The double-numeric
wave functions are used in all of the calculations.
CALCULATED CLUSTERS
(i) Ge O. The diatomic molecule is optimized for
the minimum energy for which the bond length
is found to be 1.673 and the vibrational
frequency is 922.6 cm
-1
with intensity 34.2
km/mol. The binding energy is -7.687 eV.
(ii) GeO
2
(linear). In this cluster the optimized bond
length of Ge O is 1.668 and the frequencies
(intensities) are given in Table 1.
(iii) GeO
2
(triangular). In the triangular
configuration Ge O bond length is 1.864
and O O distance is 1.629 . The various
calculated values are given in Table 1.
(iv) GeO
3
(pyramidal). In this cluster Ge O bond
length is 1.982 and O O distance is 1.926 .
(v) GeO
3
(spoke). In this cluster one Ge atom is
located in the centre and three oxygen atoms are
all around it. The Ge O bond length is 1.757.
(vi) GeO
4
(pyramidal). In this cluster, the four
oxygen atoms form a square and one Ge atom is
located on top position. The Ge O bond length
is 2.071 and O O distance is 1.797 .
(vii) GeO
4
(T
d
). In the tetrahedron coordination, the
Ge O bond length is 1.807.
(viii) GeO
5
(pyramidal). In this system all five oxygen
atoms form a pentagon and one Ge atom is
located on top position. The Ge O distance is
2.165 and O O bond length is 1.764 .
(ix) GeO
6
(pyramidal). In this case the six oxygen
atoms form a hexagon and one Ge atom is
located on top position. The Ge O bond length
is 2.244 and O O bond length is 1.697 .
RAMAN SPECTRA
We take the experimentally measured values of the
Raman frequencies from Durben and Wolf [19]. The
experimental value of 556 cm
-1
is very close to the
calculated value of 550.7 for Ge O
2
(triangular).
Similarly, the experimental value of 857 cm
-1
is very
close to the calculated value 847.5 cm
-1
formed in Ge
O
2
(triangular). The experimentally measured strong
value of 419 cm
-1
is very near the values 425.3 cm
-1

found in Ge O
3
(pyramidal). The experimentally
measured value of 520 cm
-1
is very near the calculated
value of 527.1 cm
-1
found in Ge O
5
(pyramidal).
From this we note that Ge O
2
(triangular), Ge O
3

(pyramidal) and Ge O
6
(pyramidal) clusters are
present in the vitreous Ge O
2
glassy state. Some of
the calculated clusters are shown in Fig. 1 by stick and
ball models.


Ge-O





Ge-O
2
(linear)
Ge-O2(triangular)

Ge-O
3
(pyramidal) Ge-O
3
(spoke) Ge-O
4
(pyramidal)
Ge-O
4
((T
d
) Ge-O
5
(pyramidal) Ge-O
6
(pyramidal)

FIGURE 1. Clusters of germaniumand oxygen atoms calculated from the first principles.



TABLE 1. The ab initio calculation of various values of clusters of atoms of germanium and oxygen.
S. No Cluster Frequency
cm
-1

Intensity
km/mol
Degeneracy Electronic binding
energy (eV)
1 Ge O 922.6 34.1 1 -7.687
2 GeO
2
(linear) 153.4 32.3 2 -11.336
3 989.66 52.2 1
4 GeO
2
(triangular) 536.6 14.9 1 -10.413
5 550.7 29.7 1
6 847.5 10.6 1
7 GeO
3
(pyramidal) 425.3 21.9 1 -11.302
8 438.8 4.5 2
9 703.3 21.2 1
10 GeO
3
(spoke) 119.0 12.1 1 -13.245
11 120.2 11.9 1
12 166.8 42.0 1
13 690.4 0.07 1
14 696.5 2.92 1
15 697.8 3.23 1
16 GeO
4
(pyramidal) 380.3 20.1 2 -14.133
17 396.4 37.3 1
18 684.9 8.3 1
19 GeO
4
(Td) 61.5 16.0 3 -14.454
20 636.2 3.7 3
21 GeO
5
(pyramidal) 331.3 39.9 1 -15.697
22 377.2 30.3 1
23 378.3 29.7 1
24 614.7 6.8 1
25 GeO
6
(pyramidal) 284.3 39.1 1 -18.759
26 527.1 34.3 2
27 567.5 6.5 1

CONCLUSIONS
We have calculated the vibrational frequencies in
germanium oxide clusters of atoms and we are able to
identify some of the peaks in the experimental data of
the Raman spectra of glassy material.
REFERENCES
1. J . C. Phillips, Phys. Rev. B 71, 184505 (2005).
2. M. F. Thorpe, M. V. Chubinsky, D. J . Jacobs and J . C.
Phillips, J. Non-Cryst. Solids 266-269, 859 (2000).
3. V. R. Devi, M. B. Madhari, E. L. Srihari, K. N.
Shrivastava and P. Boolchand, J. Non-Cryst. Solids 351,
489 (2005).
4. H. A. Kassim, I. A. Jalil, N. Yusof, V. R. Devi, K. N.
Shrivastava, J. Non-Cryst. Solids 353, 111 (2007).
5. N. A. J emali, H. A. Kassim, V. R. Devi, K. N.
Shrivastava, J. Non-Cryst. Solids 354, 1744 (2008).
6. A. N. Rosli, H. A. Kassimand K. N. Shrivastava, AIP
Conf. Proc. 1017, 429 (2008).
7. A. N. Rosli, H. A. Kassimand K. N. Shrivastava, AIP
Conf. Proc. 1136, 370 (2009).
8. A. N. Rosli, H. A. Kassimand K. N. Shrivastava, AIP
Conf. Proc. 1150, 376 (2009).
9. A. N. Rosli, H. A. Kassim, C. G. Jesudason and K. N.
Shrivastava, AIP Conf. Proc. 1169, 256 (2009).
10. A. N. Rosli, N. A. Zabidi, H. A. Kassimand K. N.
Shrivastava, J. Non-Cryst. Solids 356, 428 (2010).
11. A. N. Rosli, N. A. Zabidi, H. A. Kassimand K. N.
Shrivastava, J. Cluster Sci. (Springer) 21, 197 (2010).
12. M. Micoulaut, M. Malki, D. I. Novita and P. Boolchand,
Phys. Rev. B 80, 184205 (2009).
13. D. G. Georgiev, P. Boolchand and M. Micoulaut, Phys.
Rev. B 62, R9228 (2000).
14. F. L. Galeener and G. Lucovsky, Phys. Rev. Lett. 37,
1474 (1976).
15. F. L. Galeener, A. L. Leadbetter and M. W. Stringfellow,
Phys. Rev. B 27, 1052 (1983).
16. R. J . Henley, C. Meade and H. Mao, Phys. Rev. Lett. 79,
1420 (1997).
17. J . Swenson, Phys. Rev. Lett. 79, 1421 (1997).
18. Kang, S. Smolomr, T. Krauss, F. Wise, B. G. Aitken and
N. F. Borrelli, Phys. Rev. B 54, 12641 (1996).
19. D. J . Durben and G. H. Wolf, Phys. Rev. B 43, 2355
(1991).
20. W, Kohn and L. J. Sham, Phys. Rev. 140, A1133 (1965).