Electronic Oxide Polarizability and Optical Basicity of Simple Oxides. I
Electronic Oxide Polarizability and Optical Basicity of Simple Oxides. I
Electronic Oxide Polarizability and Optical Basicity of Simple Oxides. I
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)
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
Sumio Sakka
Institute for Chemical Research, Kyoto University, Gokasho, Uji-shi, Kyoto 611, Japan
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
R m5
S D
n 20 21
~ n 20 21 ! M
5
V ,
n 20 12 m
~ n 20 12 ! d
~1!
R m5
4 p a mN A
.
3
~2!
~3!
~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!
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
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
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
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!
~7!
F S AD G
Vm
a 0 22 ~ E g ! 5
12
2.52
Eg
2p a i q 21 .
20
~8!
L51.67 12
a 0 22
~9!
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
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
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
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
1740
16
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