Electronic oxide polarizability and optical basicity of simple oxides.

I
Vesselin Dimitrov and Sumio Sakka
Citation: J. Appl. Phys. 79, 1736 (1996); doi: 10.1063/1.360962
View online: http://dx.doi.org/10.1063/1.360962
View Table of Contents: http://jap.aip.org/resource/1/JAPIAU/v79/i3
Published by the American Institute of Physics.

Related Articles
Application of the Z-scan technique to determine the optical Kerr coefficient and two-photon absorption
coefficient of magnetite nanoparticles colloidal suspension
J. Appl. Phys. 111, 113509 (2012)
On conversion of luminescence into absorption and the van Roosbroeck-Shockley relation
Appl. Phys. Lett. 100, 222103 (2012)
A full Stokes vector ellipsometry measurement system for in situ diagnostics in dynamic experiments
Rev. Sci. Instrum. 83, 053904 (2012)
Nano-sized Ba2NaNb5O15NaNbO3 co-crystallized glass-ceramics in phosphoniobate system
Appl. Phys. Lett. 100, 201907 (2012)
Z-scan study of nonlinear absorption in reduced LiNbO3 crystals
J. Appl. Phys. 111, 103504 (2012)

Additional information on J. Appl. Phys.

Journal Homepage: http://jap.aip.org/
Journal Information: http://jap.aip.org/about/about_the_journal
Top downloads: http://jap.aip.org/features/most_downloaded
Information for Authors: http://jap.aip.org/authors

Downloaded 07 Jun 2012 to 128.148.252.35. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions

Electronic oxide polarizability and optical basicity of simple oxides. I

Vesselin Dimitrov
Higher Institute of Chemical Technology, Sofia-1756, Bulgaria

Sumio Sakka
Institute for Chemical Research, Kyoto University, Gokasho, Uji-shi, Kyoto 611, Japan

~Received 24 April 1995; accepted for publication 25 September 1995!

The average electronic oxide polarizability a 0 22 of numerous single component oxides has been
calculated on the basis of two different properties: linear refractive index n 0 and energy gap E g ,
which have demonstrated remarkable correlation. The optical basicity L of the oxides has been
estimated on the basis of average electronic oxide polarizability calculated from the refractive index
L~n 0! and the energy gap L(E g ). A good agreement has been observed between the optical basicity
data obtained using independent initial quantities. The simple oxides have been separated into three
groups according to the values of their oxide polarizability. The a 0 22 values ~above 3 ! obtained
for PbO, Sb2O3 , and Bi2O3 have been attributed to the high cation polarizability and the presence
of a lone pair in the valence shell of the cation. 1996 American Institute of Physics.
@S0021-8979~96!06001-1#
I. INTRODUCTION

Nonlinear optical materials have attracted much attention because of their importance for the development of optical information processing technology. For this purpose,
materials of higher optical nonlinearity have to be found or
designed on the basis of correlation of the optical nonlinearity with some other electronic properties which are easily
understandable and accessible. Since the optical nonlinearity
is caused by electronic polarization of the material upon exposure to intense light beams, polarizability is one of the
most important properties which govern the nonlinearity response of the material.
Polarizability is related to many macro- and microscopic
physical and chemical properties such as optical UV absorption of p-block metal ions,1 ionic refraction,2 4 electrooptical effect,5 dielectric properties and ferroelectricity,6,7
and chemical stability along with optical nonlinearity.8,9
Therefore, estimation of polarizability would be useful especially with respect to oxide crystals and glasses which are of
technological importance as optical and electronic materials.
On the other hand, optical basicity as proposed by Duffy
and Ingram10,11 is used as a measure of the acid-basic properties of oxides. The optical basicity can be experimentally
determined but the applicability of the method is rather limited. Hence, it is desirable to derive the values for many
oxides on the basis of the similarity in the physical nature of
the polarizability and the optical basicity.
In this article we have estimated the average electronic
oxide polarizabilities of numerous single component oxides
on the basis of two different properties: linear refractive index and energy gap and have compared the data obtained
from the two different properties. The optical basicity of the
oxides is also estimated.
II. OXIDE IONS AVERAGE ELECTRONIC
POLARIZABILITY BASED ON THE LINEAR
REFRACTIVE INDEX

The average electronic polarizability a 0 22 of a simple

oxide Ap Oq can be calculated using the LorentzLorenz
equation,3,4
1736

J. Appl. Phys. 79 (3), 1 February 1996

R m5

S D

n 20 21
~ n 20 21 ! M
5
V ,
n 20 12 m
~ n 20 12 ! d

~1!

where n 0 is the refractive index, d is the density, M is the

molecular weight, and V m is the molar volume. This equation
gives the molar refraction. By introducing Avogadros number N A , the molar refraction R m can be expressed as a function of polarizability am of a molecule,3

R m5

4 p a mN A
.
3

~2!

With am in ~3!, this equation can be transformed to

R m 52.52a m .

~3!

Assuming that R m and am are additive quantities,4 it follows

that
R m 5 pR i 1qR 0 22 52.52~ p a i 1q a 0 22 ! ,

~4!

where R i is the ionic refraction of the cation, R 0 22 is the

ionic refraction of the oxide ion, ai is the polarizability of the
cation, and a 0 22 is the polarizability of the oxide ion.
Weyl and Marboe12 have suggested that the ionic refraction of the oxide ion can be calculated by subtracting the
ionic refraction of the respective cations from the molar refraction. For the simple oxides with the general formula
Ap Oq we have calculated a 0 22 (n 0 ) using the following expression obtained on the basis of Eqs. ~1!~4!,

a 0 22 ~ n 0 ! 5

FS D

0021-8979/96/79(3)/1736/5/$6.00

V m ~ n 20 21 !
2 p a i q 21 ,
2.52 ~ n 20 12 !

~5!

1996 American Institute of Physics

Downloaded 07 Jun 2012 to 128.148.252.35. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions

TABLE I. Linear refractive index n 0 , energy gap E g , molecular weight M , density d, molar volume V m , cation
polarizability a1 , oxide polarizability a 0 22 (n 0 ), oxide polarizability a 0 22 (E g ), optical basicity L~n 0!; optical
basicity L (E g ), and optical basicity according to Duffy L ~Duffy! of simple oxides.

Oxide
Li2O
CuO
MgO
CaO
SrO
BaO
ZnO
CdO
B2O3
Al2O3
Ga2O3
In2O3
Sc2O3
Y2O3
SiO2(q)
GeO2
SnO2
PbO
TiO2(a)
TiO2(r)
ZrO2
CeO2
Sb2O3
Bi2O3
V2O5
Nb2O5
Ta2O5
TeO2
MoO3
WO3
MnO
Fe2O3
CoO
NiO

n0
1.644
2.63
1.736
1.838
1.810
1.98
2.008
2.49
1.64
1.760
1.952

1.92
1.544
1.65
1.997
2.51
2.554
2.616
2.12

2.087

2.27
2.21
2.50
2.16
3.01

2.1818

M
d
Vm
Eg
~eV! ~g/mol! ~g/cm3! ~cm3/mol!

ai
~3!

1.95
7.30
6.80
5.30
4.80
3.40
2.30

4.40
2.80
5.40

9.05
5.40
3.80
2.80
3.0
3.0
5.0
3.2
3.25
2.80
2.80
3.40
4.0
3.79
3.80
2.70
3.80
2.0
2.70
3.80

0.024
0.437
0.094
0.469
0.861
1.595
0.283
1.054
0.002
0.054
0.195
0.662
0.287
0.544
0.033
0.137
0.479
3.623
0.184
0.184
0.357
0.702
1.111
1.508
0.122
0.242
0.185
1.595
0.169
0.147
0.544
0.437
0.508
0.266

29.88
79.55
40.30
56.08
103.62
153.33
81.38
128.41
69.62
101.96
187.44
277.64
137.91
225.81
60.08
104.59
150.69
223.20
79.88
79.88
123.22
172.12
291.50
465.96
181.88
265.81
441.89
159.6
143.94
231.85
70.94
159.69
74.93
74.69

2.013
6.39
3.58
3.31
4.7
5.72
5.606
8.15
2.46
3.965
6.44
7.179
3.864
5.01
2.65
4.228
6.95
8.00
3.84
4.26
5.89
7.132
5.20
8.55
3.357
4.47
8.2
5.67
3.80
7.16
5.44
5.24
6.45
6.67

14.84
12.45
11.26
16.94
22.05
26.81
14.52
15.75
28.30
25.72
29.10
38.67
35.69
45.07
22.67
24.74
21.68
27.90
20.80
18.75
20.92
24.13
56.06
54.50
54.18
59.47
53.89
28.15
37.88
32.38
13.04
30.48
11.62
11.20

where p and q denote the number of cations and oxide ions,

respectively, in the chemical formula Ap Oq . The polarizabilities of the cations have been obtained using the ionic refraction values of Kordes,13 excepting those for Cu21, Sb31,
Bi31, and Te41 which are taken from Refs. 14 and 15. The
data on refractive index, molecular weight, and density are
also taken from the literature.16 18 A similar approach has
been applied by Duffy19,20 to several simple oxides ~P2O5 ,
B2O3 , SiO2 , Al2O3 , MgO, CaO, BaO, Li2O, TiO2 , and
ZrO2!.
The calculated polarizability values of oxide ions are
given in Table I ~column 8!. The values of a 0 22 (n 0 ) for 16
oxides ~CuO, SrO, ZnO, CdO, Ga2O5 , Y2O3 , GeO2 , SnO2 ,
PbO, Sb2O3 , TeO2 , MoO3 , WO3 , MnO, Fe2O3 , and NiO! are
given in this table in addition to those of Duffy.19,20 There is
a general trend of increase in a 0 22 (n 0 ) along with the refractive index, but the scatter of the data points is pretty large,
which indicates that no direct relation is found between
a 0 22 (n 0 ) and n 0 . This is evident from Eq. ~5! which shows
that the polarizability of the oxide ion depends not only on
the refractive index but also on the molar volume. It should
J. Appl. Phys., Vol. 79, No. 3, 1 February 1996

a 0 22 (n) a 0 22 (E g )
~3!
~2!
L(n) L(E g ) L ~Duffy!
2.090
2.838
1.699
2.505
2.918
3.652
2.612
2.909
1.345
1.365
1.732

2.458
1.401
1.720
1.908
3.450
2.584
2.368
2.054

3.172

2.444
2.769
2.677
2.303
2.647

2.202

2.963
1.675
2.334
3.382
3.830
3.105
3.078

1.913
2.762
2.075

1.454
2.287
2.191
3.311
2.438
2.188
1.897
2.522
3.686
3.507
2.643
2.679
2.291
2.358
2.769
2.662
2.357
2.467
2.405
2.218

0.87
1.08
0.69
1.00
1.10
1.21
1.03
1.10
0.43
0.45
0.71

0.99
0.48
0.70
0.79
1.19
1.02
0.96
0.86

1.14

0.99
1.07
1.05
0.94
1.04

0.91

1.11
0.67
0.95
1.18
1.23
1.13
1.13
0.42

0.80
1.07
0.87

0.52
0.94
0.91
1.17
0.98
0.91
0.79
1.01
1.22
1.19
1.04
1.05
0.94
0.96
1.07
1.04
0.96
0.99
0.98
0.92

1.00

0.78
1.00
1.10
1.15

0.42
0.60

0.48
0.60

0.95
1.0
0.90

also be remembered that the polarization of the oxide ion is

affected by the polarizing power of the cation.
III. ENERGY-GAP-BASED AVERAGE ELECTRONIC
POLARIZABILITY OF THE OXIDE ION

In the discussion on the metallization of the condensed

matter2123 it has been reported that nonmetalmetal transition occurs when R m /V m 51 @where R m is the molar refraction expressed by Eq. ~1! mentioned before#. This approach,
called the polarizability approach, indicates that when
12R m /V m becomes zero, the transition to the metal state
takes place. In the tight binding approach to the band theory,
the nonmetal to metal transition of a binary compound, such
as a simple oxide, occurs when the minimum energy for the
transfer of an electron from the anion to the cation becomes
zero.23
Taking into account the similarity in form of the criteria
in both approaches ~based on a particular quantity tending to
zero!, Duffy24 has plotted AE g ~E g : energy gap! against
12R m /V m for a large number of simple oxides and obtained
V. Dimitrov and S. Sakka

Downloaded 07 Jun 2012 to 128.148.252.35. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions

1737

FIG. 1. Oxide polarizability a 0 22 as a function of energy gap E g .

FIG. 2. Oxide polarizability a 0 22 (n 0 ) vs oxide polarizability a 0 22 (E g ).

a good linear correlation between these two distinct quantities. From the plots he has proposed the relation
E g 520~ 12R m /V m ! 2 .

~6!

Since this equation is valid for a large number of oxides,

we have used it to estimate the polarizability of the oxide ion
from the energy gap. Expression ~6! gives the explicit expression of R m ,
R m 5V m ~ 12 AE g /20! .

~7!

Substitution of Eq. ~7! in Eq. ~4! gives the polarizability

of a simple oxide with the formula Ap Oq a 0 22 (E g ),

F S AD G

Vm
a 0 22 ~ E g ! 5
12
2.52

Eg
2p a i q 21 .
20

~8!

This gives the average polarizability of the oxide ion in

an oxide calculated from the energy gap as well as the molar
volume and the polarizability of the cation.
The calculation of a 0 22 (E g ) for simple oxides has been
made by means of Eq. ~8! using energy gap data. The energy
gap data for CuO, MgO, CaO, SrO, BaO, ZnO, CdO, Ga2O3 ,
In2O3 , Sc2O3 , GeO2 , SnO2 , TiO2 , ZrO2 , CeO2 , Sb2O3 ,
MoO3 , MnO, Fe2O3 , CoO and NiO are taken from Ref. 16,
while those for Bi2O3 , Nb2O5 , V2O5 , Ta2O5 , WO3 , and PbO
are from Ref. 25. The energy gap data for SiO2 and TeO2 are
from Refs. 26 and 27, respectively. The a 0 22 (E g ) values
obtained are presented in Table I ~column 9! and plotted in
Fig. 1 as a function of the energy gap. It can be seen that, in
general, a 0 22 (E g ) increases with decreasing energy gap but
with a pretty large scattering.
The calculated values of a 0 22 (n 0 ) are plotted against
a 0 22 (E g ) in Fig. 2. A remarkable correlation is found between them. This means that the determination of oxide ion
polarizability by means of the energy gap, molar volume,
and cation polarizability of the solids is very promising.
1738

J. Appl. Phys., Vol. 79, No. 3, 1 February 1996

The literature data on the refractive index n 0 are plotted

against the literature data on the energy gap E g of numerous
simple oxides in Fig. 3. It can be seen that n 0 decreases with
increasing E g . This fact can be used for prediction of the
values of n 0 or E g for solids.
IV. OPTICAL BASICITY OF THE OXIDES

On the basis of refraction data Duffy20 has established

the following correlation:

L51.67 12

a 0 22

~9!

FIG. 3. Linear refractive index n 0 as a function of energy gap E g .

V. Dimitrov and S. Sakka

Downloaded 07 Jun 2012 to 128.148.252.35. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions

FIG. 4. Optical basicity L~n 0! vs optical basicity L(E g ).

existing between the optical basicity and the electronic polarizability of the oxide ion for silicates, aluminates, phosphates, borates, sulphates, and some simple oxides ~P2O5 ,
B2O3 , SiO2 , Al2O3 , MgO, Li2O, CaO, and BaO!.
Duffy has concluded that this relationship presents a
general tendency toward an increase in the oxide polarizability with increasing optical basicity.
Equation ~9! has been used by us for calculation of the
optical basicity L of the oxides on the basis of a 0 22 values
obtained by Eqs. ~5! and ~8!. The results are presented in
Table I ~columns 10 and 11!. New data on CuO, ZnO, CdO,
Ga2O3 , In2O3 , Sc2O3 , Y2O3 , SnO2 , Sb2O3 , Bi2O3 , V2O5 ,
Ta2O5 , TeO2 , MoO3 , WO3 , MnO, Fe2O3 , CoO, and NiO are
obtained. It is remarkable that a good correlation is found
between data obtained by us and those reported by Duffy19,20
~Table I, column 12!.
The comparative relationship between the optical basicity calculated from the refractive index L~n 0! and the optical
basicity obtained from the energy gap L(E g ) of the oxides is
plotted in Fig. 4. A good agreement can be observed between
the optical basicity data obtained with different initial quantities.
V. DISCUSSION

Detailed analysis of the average polarizabilities of the

oxide ion in simple oxides ~Table I! allows classification of
the oxides in three groups.
The first group includes SiO2 , B2O3 , Al2O3 , GeO2 , and
Ga2O3 which are characterized by a low polarizability of
oxide ion ~12 3!. Mainly p- and s-block elements belong
here. Their cations posses a low polarizability13 and most of
them have a large positive charge. Their unit field strength is
very large28 and they affect strongly the electron charge
cloud of the oxide ion.
J. Appl. Phys., Vol. 79, No. 3, 1 February 1996

The second group consists mainly of d transition-metal

oxides with an oxide polarizability between 2 and 3 3. The
relatively high polarizability of the oxide ion can be attributed to the empty d states of the corresponding cations. On
the other hand, the high coordination number ~usually 6!
toward the oxide ion in transition-metal oxides decreases the
unit field strength of the transition-metal cation. It is also of
significance that the cation polarizability of the transition
elements is relatively large.13 This decreases the polarizing
effect of the cation on the oxide ion.
The oxides of Cd21, Pb21, Ba21, Sb31, and Bi31 form
the third group having an average oxide polarizability above
3 3. These are oxides of heavy s- and p-block elements.
Their ionic radii are large ~1.411.98 !.16 The cation unit
field strength is very small: It is of the same order of magnitude as that of alkaline-earth cations.28 In addition these
cations possess a very high polarizability.13,14 It is interesting
that Pb21, Sb31, Bi31, and Te41 ions possess a lone pair in
the valence shell.29 According to Gillespie,30 repulsion works
between the different electron pairs in the coordination polyhedra of the cation. It is known that the bond-pairbond-pair
repulsion is smaller than the bond-pairlone-pair repulsion.
This may lead to an additional relaxation of the cation polarizing effect on the oxide ion. Since the cation lone pairs
~ME! distance increases from Pb21 ~1.16 ! to Sb31, ~1.18
! and Te41 ~1.26 !,29 the repulsion of the bond-pairlonepair decreases by the same order of magnitude, resulting in
an increase of the polarizing effect of the cation. The decrease of MOeq ~axial bonds! and MOeq ~equatorial
bonds! distance from PbO ~2.22; 2.19 ! to TeO2 ~2.09; 1.92
! may be regarded as supporting this assumption. This may
explain the average oxide polarizability of TeO2 which is
smaller than those for PbO, CdO, Sb2O3 and Bi2O3 .
VI. CONCLUSION

The average electronic oxide polarizability and optical

basicity have been estimated for numerous single component
oxides on the basis of two different properties: linear refractive index and energy gap. It is established that there is a
general trend of increasing a 0 22 with increasing refractive
index and decreasing energy gar. Comparison of the data
obtained from the two different properties has shown remarkable agreement.
The simple oxides have been separated into three groups
based on the oxide ion polarizability. The a 0 22 values ~above
3 3! obtained for PbO, Sb2O3 , and Bi2O3 have been explained with a high cation polarizability and the presence of
a lone pair in the valence shell of the cation.
ACKNOWLEDGMENT

One of the authors ~V.D.! would like to express his sincere gratitude to the Japan Society for the Promotion of Science ~JSPS! for providing him with financial support.
1

C. K. Jorgensen, Absorption Spectra and Chemical Bonding in Complexes

~Pergamon, Oxford, 1962!.
2
R. El-Mallawany, J. Appl. Phys. 72, 1774 ~1992!.
3
E. A. Moelwyn-Hughes, Physical Chemistry ~Pergamon, London, 1961!.
V. Dimitrov and S. Sakka

Downloaded 07 Jun 2012 to 128.148.252.35. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions

1739

H. Rawson, Properties and Applications of Glass ~Elsevier, Amsterdam,

1980!.
5
C. A. Wert and R. M. Thomson, Physics of Solids ~McGrawHill, New
York, 1964!.
6
A. Yariv and P. Yeh, Optical Waves in Crystals ~Wiley, New York, 1984!.
7
A. R. West, Solid State Chemistry and its Applications ~Wiley, New York,
1984!.
8
Materials for Nonlinear Optics ASC Symposium Series 455, edited by J.
Sohn and G. Stucky ~American Chemical Society, Washington, 1991!.
9
V. Dimitrov, S. Kim, T. Yoko, and S. Sakka, J. Ceram. Soc. Jpn. 101, 59
~1993!.
10
J. Duffy and M. Ingram, J. Am. Chem. Soc. 93, 6448 ~1971!.
11
J. Duffy and M. Ingram, J. Non-Cryst. Solids 21, 373 ~1976!.
12
W. A. Weyl and E. G. Marboe, The Constitution of Glasses ~WileyInterscience, New York, 1962!.
13
E. Kordes, Z. Phys. Chem. B 44, 249 ~1939!.
14
A. Appen, Chemistry of the Glass ~Chimija, Leningrad, 1970!.
15
A. K. Yakhkind, J. Am. Ceram. Soc. 47, 42 ~1966!.
4

1740

J. Appl. Phys., Vol. 79, No. 3, 1 February 1996

16

Handbook of Chemistry and Physics, 62nd ed, edited by R. C. Weast

~Chemical Rubber Co., Boca Raton, 1981!.
17
R. Adair, L. Chase, and S. Payne, Phys. Rev. B 39, 3337 ~1989!.
18
J. Liebertz, Kristall. Technik Bd. 4, 221 ~1962!.
19
J. Duffy, J. Am. Ceram. Soc. 72, 2012 ~1989!.
20
J. Duffy, Phys. Chem. Glasses 30, 1 ~1989!.
21
K. Herzfeld, Phys. Rev. 29, 701 ~1927!.
22
P. Edwards and M. Sienko, Chem. Brit. Jan. 39 ~1983!.
23
P. Edwards and M. Sienko, Int. Rev. Phys. Chem. 3, 83 ~1983!.
24
J. Duffy, J. Solid State Chem. 62, 145 ~1986!.
25
A. Nozik, Ann. Rev. Phys. Chem. 29, 189 ~1978!.
26
H. Philipp, J. Phys. Chem. Sol. 32, 1935 ~1971!.
27
N. Uchida, Phys. Rev. B 4, 3736 ~1971!.
28
K. H. Sun, J. Am. Ceram. Soc. 30, 277 ~1947!.
29
J. Galy, G. Mennier, S. Andersson, and A. Astrom, J. Solid State Chem.
13, 142 ~1975!.
30
R. J. Gillespie, Molecular Geometry ~Van Nostrand Reinhold, London,
1972!.

V. Dimitrov and S. Sakka

Downloaded 07 Jun 2012 to 128.148.252.35. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions