Spectrochimica Acta Part A 79 (2011) 1251–1255

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Ab initio calculation of vibrational frequencies and Raman spectra of barium

peroxide glass including comparison of tetrahedral BaO4 with GeO4 and SiO4
Ahmad Nazrul Rosli, Noriza Ahmad Zabidi, Hasan Abu Kassim, Keshav N. Shrivastava ∗
Department of Physics, University of Malaya, Kuala Lumpur 50603, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: We have calculated the vibrational frequencies of clusters of atoms from the first principles by using
Received 14 February 2011 the density-functional theory in the local density approximation (LDA). We are also able to calculate the
Received in revised form 5 April 2011 electronic binding energy for all of the clusters of atoms from the optimized structure. We have made
Accepted 18 April 2011
clusters of Ban Om (n, m = 1–6) and have determined the bond lengths, vibrational frequencies as well as
intensities in each case. We find that the peroxide cluster BaO2 occurs with the O–O vibrational frequency
PACS:
of 836.3 cm−1 . We also find that a glass network occurs in the material which explains the vibrational
61.43.Fs
frequency of 67 cm−1 . The calculated values agree with those measured from the Raman spectra of barium
63.50.−x
78.30.−jAmorphous metals
peroxide and Ba-B-oxide glass. We have calculated the vibrational frequencies of BaO4 , GeO4 and SiO4
Metallic glasses each in tetrahedral configuration and find that the vibrational frequencies in these systems depend on
Barium peroxide the inverse square root of the atomic mass.
Raman scattering © 2011 Elsevier B.V. All rights reserved.

1. Introduction of electrons. Since we know the Hamiltonian from first principles,

Recently, it was pointed out by Phillips [1] that microscopi-
cally homogeneous glasses are in a metastable state. They exhibit
structural transitions below a glass transition temperature, Tg . The
relaxation times, , are characterized by a stretched exponen-
tial with decay probability, exp − (t/)ˇ and the viscosity diverges
at the glass transition temperature Tg as  ∝ exp[T/(T − Tg )]˛ with
˛  (1.5)5 . Some of the glasses contain a network of atoms which
exhibit selfsimilarity [2]. This type of selfsimilarity is often found
in oxides and chalcogenides which show a phase transition in the
rigidity [3]. There is a phase in which bonds are floppy while in
the other phase, bonds become rigidly tied [4]. We have found that
clusters of atoms are present in the glassy state and it is possi-
ble that random arrangement of clusters of atoms are connected
by random bonds. We have found that the calculated values of
the vibrational frequencies are in agreement with those measured
by the Raman spectra of GeSI [5], GePS [6], GeSe [7] and AsO [8]
glasses. In some cases the clusters are bound by a back bone char-
acterized by a linear chain. We have also performed the ab initio
calculation of the vibrational frequencies in AsSe [9], AsS [10], FeAs
[11] and CN [12] clusters of atoms which indicate the formation
of randomly connected clusters of atoms in the glasses. Some time
ago, Kohn and Sham [13] have written the quantum mechanical
Schrödinger equation in terms of coordinate dependent density
∗ Corresponding author: Tel.: +60 3 7967 7140; fax: +60 3 7967 4146.
E-mail address: keshav1001@yahoo.com (K.N. Shrivastava).
we can computerize large secular determinants by using the local-
density approximation (LDA). Hence, it is possible to determine the
structures and bond lengths by optimization of the energy of the
Schrödinger equation. We separated the equations for the elec-
tron motion as well as for the motion of the nuclei from which
we determined the vibrational frequencies which are of interest
to understand the vibrational as well as the Raman spectra. Usu-
ally, in a single crystal, the usual transverse and longitudinal optical
modes (TO and LO) are found. It is also possible to find the trans-
verse and the longitudinal acoustic modes (TA and LA). However,
in molecules and in the amorphous state, the problem is quite dif-
ferent. We have found that the amorphous state often consists of
clusters of atoms which are found in glassy form.
The barium oxide is known to occur in rocksalt structure, space
group Fm3m , BaO(I). When pressure ≥10 GPa is applied, it changes
the structure to hexagonal cell of NiAs type, space group P63 /mmc,
c /a = 1:0.75. This phase is called BaO(II). The oxygen atoms are
at (0, 0, 0) and (0, 0, 1/2) and Ba atoms are at (1/3, 2/3, 1/4) and
(2/3, 1/3, 3/4). When pressure is larger than 18 GPa up to 60.5 GPa,
a third phase occurs which is tetragonal PH4 I type, P4/nmmm [14].
The reflectivity of BaO has been reported [15] and the photoemis-
sion spectra have also been studied [16]. It shows strain-induced
ferroelectricity [17] in simple rock salt structure. The charge trans-
fer from 4d10 (1 So) to 4d9 4f 1 (3 P1) and 4d9 4f 1 (3 D1) states has been
found by using synchrotron radiation of energy 92–97 eV [18]. The-
oretical simulation of clusters of Ba atoms has been done by Wang
et al. [19] who find the magic number of Ba atoms in a cluster for
which the cluster is stable. Low frequency Raman spectra of

1386-1425/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2011.04.051
1252 A.N. Rosli et al. / Spectrochimica Acta Part A 79 (2011) 1251–1255

barium borate glasses in the system
(BaCl2 )y [(BaO)x (B2 O3 )1−x−y ]1−y show bands at 67, 116 and
140 cm−1 . Most likely, the 67 cm−1 is associated with glass net
work while 116 and 140 cm−1 bands are due to the borate group
[20]. A detailed study of the Raman spectra of barium peroxide is
given by Haller et al. [21] who find that A1g O–O stretching mode
occurs at 830 cm−1 by using 515.4 nm and 532.1 nm argon ion
laser. There is a strong band at 838 cm−1 but there are also present
weak lines at 826 cm −1 and 814 cm−1 . It is not clear whether the
weaker lines are associated with impurities such as Sr and Ca.
The best application of barium is found in copper-oxide based
superconductors where Ba doping induces superconductivity.
Doping yttrium–barium–copper oxide by lanthanum induces
superconductor–insulator transition due to strong compensation
of dopants [22]. A first principles study [23] shows that BaO can
become ferroelectric.
In this paper, we report our study of the clusters of mixed Ba and
O atoms as determined by the optimization of the bond lengths. We
are able to predict the correct vibrational frequency of O2 molecule
as in barium peroxide, BaO2 , the experimental value of which is
830 cm−1 . We also report our calculation of the vibrational fre-
quencies of BaO4 , GeO4 and SiO4 in tetrahedral symmetry which
show the strong effect of the inverse square root of the atomic
mass.
2. Methodology
We use the density-functional theory to calculate the vibrational
frequencies in a cluster of atoms. The full electronic configuration
is used and there are no pseudopotentials in our calculation. We
use the local density approximation (LDA) in all of the calcula-
tions given here. The computer programme is the DMol3 of Accelrys
Software Inc., San Diego, CA, USA. It is the “windows” version run
on quadro pentium computer.We can choose any of the follow-
ing wave functions. The “min” selects only one Slater orbital on
each atom which is occupied. The double numeric (DN) means at
least two atomic orbitals for each one occupied in the free atom.
The “DNP” means DN with polarization. The DND chooses double-
numerical+d-DNP basis except that no p wave functions are used
on hydrogen. There are several options but the DN gives values

Table 1
The vibrational frequencies, intensities, degeneracies and electronic binding energy of clusters calculated from the first principles.

S. no. Cluster Frequency Intensity Degeneracy Electronic

(cm−1 ) (km/mol) energy (eV)

1. BaO 359.6 12 1 −3.26

2. BaO2 (linear) 62.9 117.9 2 −7.39
3. 278.7 0.0 1
4. 362.9 3.5 1
5. BaO2 (triangular) 269.0 9.8 1 −8.47
6. 313.8 0.3 1
7. 836.3 357.1 1
8. BaO3 (spoke) 51.7 29.8 2 −8.83
9. 69.3 88.9 1
10. 258.3 0.0 1
11. 304.1 0.35 2
12. BaO3 (pyramidal) 220.1 29.1 1 −10.34
13. 326.4 0.01 2
14. 508.2 140.1 1
15. BaO4 (pyramidal) 290.7 51.3 1 −14.551
16. 301.5 3.8 2
17. 343.7 0.0 1
18. 611.8 1.45 1
19. BaO4 (Td ) 28.0 0.0 1 −9.061
20. 51.3 35.6 3
21. 232.7 0.0 1
22. 256.8 0.1 3
23. OBa2 (triangular) 59.0 5.2 1 −4.924
24. 278.4 38.05 1
25. 443.9 0.78 1
26. OBa3 (spoke) 19.0 0.16 2 −5.797
27. 88.5 4.31 1
28. 119.5 2.16 1
29. 379.5 10.0 2
30. OBa3 (pyramidal) 60.8 0.35 2 −6.001
31. 92.0 2.88 1
32. 204.7 7.23 1
33. 446.7 6.1 2
34. OBa4 (Td ) 72.6 0.02 3 −6.025
35. 128.5 0.00 1
36. 326.2 15.6 3
37. OBa4 (square) 111.3 1.23 2 −6.271
38. 111.9 0.0 1
39. 114.3 0.0 1
40. 163.8 0.06 1
41. 212.3 37.8 2
42. OBa5 (pyramidal) 32.2 0.0 1 −7.083
43. 36.0 0.6 2
44. 74.6 0.2 2
45. 77.7 0.0 2
46. 98.9 0.15 1
47. 101.4 0.0 1
48. 283.5 44.0 2
 A.N. Rosli et al. / Spectrochimica Acta Part A 79 (2011) 1251–1255
which agree with the experimental data. The DN wave functions are
used throughout in most of the calculations performed by us. We
have used a serial number for every vibrational frequency which is
denoted by S. no. in Table 1. The intensities are usually described by
arbitrary units. However, the computer programme calculates the
intensities in the kilometer per molecule (km/mol) units consistent
with the IUPAC recommendation.
3. Results and discussion
3.1. Clusters
We make the clusters of mixed Ba and O atoms. The clusters of
pure Ba atoms are not very stable due to the metallic character of
barium. The clusters of mixed Ba and O atoms are very stable as
indicated by their large negative binding energy.
(i) BaO (diatomic molecule). The optimized bond length is found
to be 2.423 Å. There is a strong stretching frequency at
359.6 cm−1 with intensity 12.0 km/mol. The binding energy
is −3.26 eV.
(ii) BaO2 (linear). In this system the Ba–O bond length is 2.458 Å
and the binding energy is −7.392 eV. The vibrational frequen-
cies (intensities) are given in Table 1.
(iii) BaO2 (triangular). In this system the O–O bond length is
1.502 Å and for Ba–O it is 2.561 Å. The vibrational frequencies
are given in Table 1.
(iv) BaO3 (spokes). There is one atom of Ba in the centre and the
three oxygen atoms are connected with three bonds one each
to the central Ba. The Ba–O bond length is 2.571 Å.
(v) BaO3 (pyramidal). The three oxygen atoms form a triangle and
one O atom is on top. The Ba–O distance is 2.524 Å and O–O
distance is 1.949 Å.
(vi) BaO4 (pyramidal). The four oxygen atoms form a square and
one Ba atom is on top position. The Ba–O bond length is found
to be 2.577 Å and O–O distance is 1.792 Å.
(vii) BaO4 (Td ). In the tetrahedral configuration with one Ba in the
centre and four O atoms forming a tetrahedron, the Ba–O bond
length is 2.661 Å. The calculated values are given in Table 1.
The clusters of BaOn (n = 1–4) are shown in Fig. 1.
Fig. 1. The clusters of BaOn (n = 1–4) shown by stick-ball models. All of these clusters are stable.
1253
(viii) OBa2 (triangular). This molecule has a Ba–O bond length of
2.412 Å and Ba–Ba distance is 4.003 Å.
(ix) OBa3 (spoke). One O atom is in the centre and three Ba atoms
are all around it. The Ba–O distance is 2.507 Å.
(x) OBa3 (pyramidal). In this pyramidal configuration, the Ba–O
distance is 2.427 Å and Ba–Ba bond length is 3.995 Å. The com-
puted frequencies are given in Table 1.
(xi) OBa4 (Td ). The tetrahedral configuration has the bond length
of Ba–O equal to 2.596 Å.
(xii) OBa4 (square). In this cluster one O atom is located in the cen-
tre of a square and Ba atoms are located on the corners of a
square. The Ba–O bond length is 2.783 Å and Ba–Ba distance
is 3.935 Å.
(xiii) OBa5 (pyramidal). The four Ba atoms are located on the corners
of a square and one Ba atom is in the centre of the square. The
O atom is on top position. The Ba–O bond length is 2.598 Å and
Ba–Ba distance is 4.194 Å. The clusters of OBan (n = 1–6) are
shown in Fig. 2 by stick-ball models.
There is a strong electron–phonon interaction in the solid state
whereas molecules have only localized oscillations. The molecular
vibrations are very strong in the Raman spectra whereas crys-
tal lattice effects appear in solids. Hence, the Jahn–Teller effect
favors isomers in the molecules. The BaO3 (spoke) at −8.83 eV is
less stable than BaO3 (pyramidal) which is at −10.34 eV. Similarly,
the BaO4 (pyramidal) at −14.551 eV is more stable than BaO4 (Td )
which has the binding energy of −9.061 eV. Thus, in atomic beams
and in glasses, several clusters of atoms are predicted.
3.2. Tetrahedral BaO4 , GeO4 and SiO4
We have calculated the vibrational frequencies of the tetrahe-
dral BaO4 , GeO4 and SiO4 by using the double numeric (DN) wave
functions which are given in Table 2. The bond length in the BaO4
tetrahedron is 2.704 Å which is the largest amongst the three tetra-
hedrons. The bond length in GeO4 is 1.849 Å and in SiO4 it is 1.745 Å.
The atomic numbers of Ba, Ge and Si are 56, 32 and 14, respectively,
indicating the uniform expansion of bonds as a function of atomic
numbers. Similarly, the vibrational frequencies are proportional to
the inverse square root of the atomic mass.
1254 A.N. Rosli et al. / Spectrochimica Acta Part A 79 (2011) 1251–1255
Fig. 2. The clusters of OBan (n = 1–5) shown by stick-ball models.
3.3. Instabilities and negative frequencies
Some of the clusters are not stable but can be stabilized upon
shining with strong radiation. The frequencies of some of the modes
become negative so that energy has to be supplied for these modes
to be observed. The negative energy indicates that these modes will
occur as sum of the frequencies. For example, usually, E1 − E2 = h.
When one of the energies is negative, the formula is changed to,
E1 − (−E2 ) = h which is equivalent to a sum process quite per-
mitted in actual experiment. Out of the 13 clusters given above,
all of them give positive frequencies as tabulated. However, three
clusters gave a negative value in addition to the positive val-
ues. BaO3 (pyramidal) gives one negative frequency(intensity) as
−607.1 cm−1 (38.6), BaO4 (pyramidal) gave two negative values,
−384.6(81.2(2)) and −241.9 cm−1 (0.0) and OBa5 has one neg-
ative value, −206.8 cm−1 (8.09). It may be noted that some of
the frequencies come with zero intensity. Thus BaO3 (pyramidal),
BaO4 (pyramidal) and OBa5 are in a different class than the usual
stable clusters of atoms.
3.4. The Raman spectra
A very detailed experimental study of the Raman spectra of bar-
ium peroxide is performed by Haller et al. [21]. In this study, the
Table 2
The vibrational frequencies, intensities (degeneracies) for the tetrahedrons of BaO4 , GeO4 and SiO4 calculated from the first principles.
S. no. BaO4
−1
Frequency (cm ) Intensity
(degeneracy)
(km/mol)
1. 52.2 28.1(3)
2. 253.3 0.05(3)
O–O stretching frequency is found to be 838 cm−1 which is a strong
peak. We have calculated the value of O–O stretching frequency
of 836.3 cm−1 for BaO2 (triangle) given in line 7 of Table 1. The
calculated value is in good agreement with the measured value.
This agreement builds confidence in the calculations. The value
reported by de Waal et al. [23] varies between 843 and 853 cm−1 .
Rahman et al. [20] have reported the low frequency Raman spec-
tra of borate glasses in the system (BaCl2 )y [(BaO)x (B2 O3 )1−y−x ]1−y .
The bands at 116 and 140 cm−1 are ascribed to the vibrational
motion of the borate group and the 67 cm−1 to structural correla-
tions of the glass network. We see from Table 1 that our calculated
frequency for BaO3 (spoke) is 69.3 cm−1 which is quite close to
the measured value of 67 cm−1 . We thus find that our calcula-
tions help in identification of clusters of atoms present in the
glass. The spoke type bonds occur in the network glasses. In the
case of Ag–Sb based thermoelectric material also the first princi-
ples calculations of the gap energies are found to be useful [24].
In the case of PbTe the calculation gives the information about
defects [25]. Chen et al. [26] have shown that bond breaking in
Si–O can be explained from the first-principle calculations. In the
case of barium peroxide it is found that only a small number of
atoms are sufficient to explain the peak observed in the Raman
spectra.
GeO4 SiO4
−1
Frequency (cm ) Intensity Frequency (cm−1 ) Intensity
(degeneracy) (degeneracy)
(km/mol) (km/mol)
139.5 14.5(3) 224.3 18.4(3)
539.8 0.08(8) 709.1 0.16(3)
 A.N. Rosli et al. / Spectrochimica Acta Part A 79 (2011) 1251–1255
4. Conclusions
We have calculated the vibrational frequencies of several clus-
ters of barium and oxygen atoms from the first principles and from
that we are able to identify the existence of peroxide, BaO2 , cluster
as well as a network glass involving BaO3 type structure. We have
also calculated the vibrational frequencies in tetrahedral clusters of
BaO4 , GeO4 and SiO4 from which we have found that the vibrational
frequencies are strongly affected by the atomic mass.
Acknowledgments
We are grateful to the Malaysian Academy of Sciences for the
award of a project from the Scientific Advancement Grants Allo-
cation (SAGA). We wish to thank the Ministry of Higher Education
for the award of Fundamental Research Grants Scheme (FRGS). We
also express our gratitude to the University of Malaya for support
of research in condensed matter physics through the University of
Malaya Research Grants (UMRG).
References
[1] J.C. Phillips, Phys. Rev. B 73 (2006), 104206–1-6.
[2] J.C. Phillips, Phys. Rev. B 73 (2006), 024210–1-10.
[3] P. Boolchand, G. Lucovsky, J.C. Phillips, M.F. Thorpe, Philos. Mag. 85 (2005)
3823–3838.
[4] M.T.M. Shatnawi, C.L. Farrow, P. Chen, P. Boolchand, A. Sartbaeva, M.F. Thorpe,
S.J.L. Billinge, Phys. Rev. B 77 (2008), 094134–1-11.
1255
[5] V.R. Devi, M.B. Madhavi, E.L. Srihari, K.N. Shrivastava, P. Boolchand, J. Non-Cryst.
Solids 351 (2005) 489–494.
[6] H.A. Kassim, I.A. Jalil, N. Yusof, V.R. Devi, K.N. Shrivastava, J. Non-Cryst. Solids
353 (2007) 111–118.
[7] N.A. Jamali, H.A. Kassim, V.R. Devi, K.N. Shrivastava, J. Non-Cryst. Solids 354
(2008) 1744–1750.
[8] A.N. Rosli, N.A. Zabidi, H.A. Kassim, K.N. Shrivastava, J. Non-Cryst. Solids 356
(2010) 428–433.
[9] A.N. Rosli, H.A. Kassim, K.N. Shrivastava, AIP Conf. Proc. 1017 (2008) 429–
433.
[10] A.N. Rosli, H.A. Kassim, K.N. Shrivastava, AIP Conf. Proc. 1136 (2009) 370–
374.
[11] A.N. Rosli, H.A. Kassim, C.G. Jesudason, K.N. Shrivastava, AIP Conf. Proc. 1169
(2009) 256–260.
[12] A.N. Rosli, N.A. Zabidi, H.A. Kassim, K.N. Shrivastava, J. Clust. Sci. 21 (2010)
197–210.
[13] W. Kohn, L.J. Sham, Phys. Rev. 140 (1965) A1133–A1138.
[14] S.T. Weir, Y.K. Vohra, A.L. Ruoff, Phys. Rev. B 33 (1986) 4221–4226.
[15] F.C. Jahoda, Phys. Rev. 107 (1957) 1261–1265.
[16] H.R. Phillipp, Phys. Rev. 107 (1987) 687–693.
[17] E. Bousquet, N.A. Spaldin, P. Ghosez, Phys. Rev. Lett. 104 (2010), 037601–1-4.
[18] C.-N. Chang, H.-F. Liu, C.-H. Hsieh, J.-M. Chen, Phys. Rev. B60 (1999) 7703–7706.
[19] Q. Wang, Q. Sun, J.-Z. Yu, B.-L. Gu, Y. Kawazoe, Y. Hashi, Phys. Rev. A 62 (2000),
063203–1-6.
[20] M.H. Rahman, B.P. Dwivedi, Y. Kumar, B.N. Khanna, Spectrochim. Acta A 49
(1993) 995–1001.
[21] K. Haller, J.H. Lunsford, J. Laane, J. Phys. Chem. 100 (1996) 551–555.
[22] M. Müller, B.I. Shklovskii, Phys. Rev. B 79 (2009), 134504–1-12.
[23] D. de Waal, K.-J. Range, M. Konigstein, W. Kiefer, J. Raman Spectrosc. 29 (1998)
109–113.
[24] K. Hoang, S.D. Mahanti, J.R. Salvador, M.G. Kanatzidis, Phys. Rev. Lett. 99 (2007),
156403–1-4.
[25] K. Hoang, S.D. Mahanti, P. Jena, Phys. Rev. B 76 (2007), 115432–1-18.
[26] Y.-C. Chen, Z. Lu, K.-i. Nomura, W. Wang, R.K. Kalia, A. Nakano, P. Vashishta,
Phys. Rev. Lett. 99 (2007), 155506–1-4.