Journal of the Physical Society of Japan

Vol. 76, No. 6, June, 2007, 065001

#2007 The Physical Society of Japan SHORT NOTES

0.4
Temperature Dependence of Raman Scattering
1
Pb(NO3)2
Spectra in Lead Nitrate Crystal
Lattice Modes
1  Room temperature
Hiroshi I SODA, Akira SAKAI , and Riki K AWASHIMA

Intensity (arb. units)

Department of Materials Science and Engineering,
Muroran Institute of Technology, Muroran, Hokkaido 050-8585 0.3
1
Department of Electrical and Electronic Engineering,
Muroran Institute of Technology, Muroran, Hokkaido 050-8585 4
(Received November 13, 2006; accepted April 18, 2007;
published May 25, 2007) Unknown
2 2
KEYWORDS: lead nitrate crystal, Raman spectra, transition phe-
nomena
0.2
DOI: 10.1143/JPSJ.76.065001

Thermal hysteresis in a lead nitrate Pb(NO3 )2 crystal with

0 500 1000 1500 2000
cubic symmetry1) was studied by using both electric2) and
-1
thermal measurements.3) A appreciable temperature varia- Raman Shift (cm )
tion was observed in the temperature region between 240
Fig. 1. Raman spectrum of the single Pb(NO3 )2 crystal at room temper-
and 300 K.2,3) However, electric,4) elastic,5) X-ray Debye ature.
temperature,6) thermal properties,7) and Raman scattering8)
measurements found no evidence for structural transitions
from 80 to 575 K. The previous Raman spectra for lead
nitrate were observed only at 80,9) 300, and 485 K.8) To
clarify unknown characteristic features concerning the Pb(NO3)2
300 K
dynamics of both lattice vibrations and molecules in the
Pb(NO3 )2 single crystal, Raman scattering study was carried
6
out in the temperature region from 200 to 300 K by the Cooling
micro-Raman technique. 285 K
The single crystal was grown in an aqueous solution
of lead nitrate by the slow evaporation method at
Intensity (arb. units)

ð313:2 { 312:5Þ  0:5 K in 456 h. The Raman-scattering

273 K
measurements were performed in the back scattering con- 4
figuration at the sample growth surface. The experimental
procedures were given in ref. 10. The 532 nm line of the
Nd:YVO4 laser was focused on a spot with diameter of 260 K
2 mm on the sample surface. The damage caused to the
sample by the incident laser beam was not observed during
the measurement. The thickness of the sample is 0:095  240 K
2
5 cm. The temperature was controlled to within 0:1 K and
the spectral resolution was set to about 2 cm1 . The observed
220 K
spectra were fitted to a Lorentzian line shape. Frequencies,
line-width, and the integrated intensities of the observed
200 K
peaks were obtained by a least square method.
The direction of an incident laser beam is parallel to the
50 100 150 200
crystallographic C3 axis such that the electric field of the -1
incident beam is parallel to the molecular plane of the Raman Shift (cm )
nitrate ion. The centrosymmetric structure of Pb(NO3 )2 is Fig. 2. Temperature dependence of Raman spectra in the region from 40
space group Th6 with four molecular units per primitive to 200 cm1 for the single Pb(NO3 )2 crystal.
cell. According to group theoretical analysis, there are 105
fundamental vibrations divided into 48 internal vibrations
and 57 external vibrations.9,11) to 200 cm1 . Figure 3 also shows the temperature depend-
A typical Raman spectrum in the wide frequency region ence of the 1 internal mode from 1030 to 1070 cm1 . The
was shown in Fig. 1 at room temperature. The 1 and 4 observed peaks were well fitted to the Lorentzian function.
internal modes of nitrate ion are clearly observed. The The peak positions of the lattice mode and the internal 1
forbidden 22 mode appeared in the Raman spectrum mode are given in Figs. 4(a) and 4(b), respectively. The
because of a non-linear effect. temperature dependence of full width at half maximum
The Raman spectra of lattice modes are shown in Fig. 2 as (abbreviated as FWHM) for these modes is shown in Fig. 5.
a function of temperature in the frequency regions from 40 As seen in these figures, the peak positions and widths of
both the internal and lattice modes show a monotonical

Corresponding author. temperature dependence. That is, no anomalous behavior
065001-1
J. Phys. Soc. Jpn., Vol. 76, No. 6 SHORT NOTES H. ISODA et al.

14
15 Pb(NO3)2 Cooling Pb(NO3)2
1 300 K
12

285 K

Half-width (cm-1)
10
Lattice vibration
10
Intensity (arb. units)

273 K Cooling
8 Heating

260 K
1
6
5 240 K

4
220 K
200 220 240 260 280 300
T(K)
200 K
Fig. 5. Full width at half maximum (abbreviated as FWHM, cm1 ) for the
0 lattic and 1 internal modes as a function of temperature in cooling ( )
1030 1040 1050 1060 1070
and heating ( ) processes for the Pb(NO3 )2 crystal.
Raman shift (cm-1)

Fig. 3. Temperature dependence of Raman spectra in the region from

1030 to 1070 cm1 for the single Pb(NO3 )2 crystal. The peak in the real part  0 ðTÞ for the complex
conductivity   ðTÞ along [111] was observed near 275 K
in the first heating measuring run in the electrical measure-
100 ment.2) A broad temperature variation of  0 ðTÞ was also
found at temperatures between 240 and 210 K.2) The
(a)
Peak position (cm-1)

98 temperature variation with a thermal hysteresis of heat

capacity was observed in the temperature region between
96
230 and 290 K by ac calorimetry.3) The maximum peak
94 Lattice vibration in the heat capacity at 275.22 K was observable only in
the heating processes of both the first and the second runs.
92 A broad temperature variation was observed in the heat
capacity at temperatures T between 230 and 260 K in
90
200 220 240 260 280 300 he cooling process of the second run. However, the
T(K) temperature variations in line shapes of Raman spectra
were not detected in comparison with those found in both
1030 electric and thermal measurements.2,3) Therefore, it is
Peak position (cm-1)

(b) concluded that the observed transition-like phenomena

1 would be related to the complex dynamics involved in a
1040 lead nitrate crystal.

1050 1) H. Nowotny and G. Heger: Acta Crystallogr., Sect. C 42 (1986) 133.

2) H. Isoda and R. Kawashima: Phys. Status Solidi B 244 (2007) 794.
3) H. Isoda and R. Kawashima: J. Phys. Chem. Solids 68 (2007) 561.
4) Y. A. Badr and R. Kamel: J. Phys. Chem. Solids 41 (1980) 1127.
1060 5) F. Michard: Phys. Rev. B 24 (1981) 4253.
200 220 240 260 280 300
6) R. G. Kulkarni and G. K. Bichile: Acta Crystallogr., Sect. A 31 (1975)
T(K) 619.
7) O. Bjorseth, J. H. Fermor, and A. Kjekshus: Acta Chem. Scand. 25
Fig. 4. Raman peak frequencies for the lattice mode (a) and the 1 mode (1971) 3791.
(b) in Pb(NO3 )2 as a function of temperature in cooling ( ) and heating 8) M. H. Brooker: J. Solid State Chem. 28 (1979) 29.
( ) processes. 9) M. H. Brooker and J. B. Bates: Spectrochim. Acta, Part A 29 (1973)
439.
10) E. Islam, A. Sakai, and A. Onodera: J. Phys. Soc. Jpn. 71 (2002) 1594.
exists. The temperature dependence of the peak position is 11) A. M. Bon, C. Benoit, and O. Bernard: Phys. Status Solidi B 78
explained well by the thermal expansion. (1976) 67.

065001-2