Study of the complex vibrational

spectra of natural zeolite chabazite

F. Pechar and D. Rykl

Czechoslovak Academy of Sciences, Institute of Geology and Geotechnics,

V Hole~ovidkhch 41, 182 09 Praha 8, C>.echoslovakia
(Received 23 November 1982)

The vibrational spectra of the natural zeolite chabazite (locality l~ep~ice, Bohemia were
measured in the infrared (200-4000cm -1) and the far-infrared (40-400 cm -1) region; the
infrared reflectance (200-1400 cm -l) and Raman scattering (50-4000 cm -~) spectra of the
polycrystalline material were also measured.
The Schimanouchi 1 GCCC, BGLZ and LSMA programs were used to calculate the force
constants and theoretical vibrational frequencies of the Si-O, AI-O, O-Si-O, O-AI-O,
Si(AI)-O-Si, O-H, H-O-H, libration H20 , and cation-oxygen bond on the basis of the
symmetry coordinates. The KKK-1 program 2 was used to calculate the dispersion curves of
the complex refractive index for both parts of the complex dielectric permittivity in the
whole measured wavenumber region. The bands in the spectra were assigned to the vibrations
of the individual bonds and structural groups of the chabazite on the basis of theoretical
calculations.
Keywords: Chabazite;complex vibrational spectra-infrared absorption;infrared reflection and Raman
scattering

EXPERIMENTAL
'File infrared absoq)tion spectra o f chabazite,
having an ideal crystallochcmical formula of
Ca2AlaSisO24.13H20 (loc~flity Rep(:ice, Bohemia)
were measured in the wavenumber region 2004000 cm -1 on a double-beam Perkin-Elmer 325
spectrometer, fitted with a grating monochromator.
Samples of the crystalline material were prepared
in KBr pellet (1:40) and the spectra were measured
at normal temperature and pressure (Figure 1)6.
The far-infrared absorption polarization spectra at
wavenumber region of 4 0 - 4 0 0 cm -1 were measured
using a Beckman FS-720 interferometer (Fzigure 2 ).
Samples were prepared in polyethylene foil (1 : 20)
at 200C and measured in vacuo (oil pump) at
normal temperature. The spectra evaluated by the
Fourier method on a computer.
The rellectance polarization spectra in the wavenumber region of 200-1400 cm -i were measured
using a Perkin-Elmer 325 spectrometer, both at
normal temperature and pressure (Figure 3).
Samples were prepared as optically polished
crystals of chabazite. The reflectance walue (%R)
was measured in steps of 5 cm -1 relative to an AImirror and were treated by the KKK-1 a for computation of the dispersion curves of the complex
dielectric permittivity and complex refractive
index (Figures 4-6).
The Raman scattering polarization spectra of the
polycrystalline sample were measured on a SPEX
14018 laser Raman spectrometer (Xar- = 514.5 nm)
0144-2449/83/040333-04503.00
Butterworth & Co. (Publishers) Ltd.

at normal temperature and pressure in the wavenumber region 5 0 - 4 0 0 0 cm -l (Figure 8). Samples
were prepared for measurement by cementing the
crystals to a quartz rod.
Chemical quantitative analyses of the chabazite
samples are listed in Table 1. Table 2 gives evaluation of all the studied vibrational spectra. The
results of calculation of the theoretical frequencies
and force constants of the bonds and of the GCCC,
LSMA and BGLZ programs I are listed in Table 3.
Preparation of the data for computation is described in many publications 3-s.

DISCUSSION
All the studied spectra yielded readily distinguishable vibrational bands with a relatively low background. The precision of the measurement of the
individual band wavenumbers in all the studied
spectra was -+(2-5)cm -1. The studied spectra can
I00

o~

0
4000

3000

2000

1600

1200

800

400

cm-I

Figure 1

Infrared absorption spectra (200-4000 cm -~) of natural

chabazite

ZEOLITE& 1983, Vol. 3, October

333

Study o f the complex vibrational spectra o f natural zeolite -- chabazite: F. Pechar and D. R y k l

6 D

60

5 -

3
40
2

0
200
20 m

I
400

[
600

I
800

I000

1200

1400

crn -I
Figure 5
Dispersion c u r v e of t h e reaJ p a r t c o m p l e x d i e l e c t r i c
p e r m i t t i v i t y of natural c h a b a z i t e

-t

400

300

200

100

cm -I
Figure 2

F a r - i n f r a r e d spectra ( 4 0 - 4 0 0 c m -~) o f natural chabazite

2

AL
80

Q:

0
200

6 0 --

400

600

800

1000

1200

1400

cm -I
40

Figure 6
Dispersion c u r v e o f the i m a g i n a r y Dart c o m p l e x
d i e l e c t r i c p e r m i t t i v i t y o f natural c h a b a z i t e

20 -

0
1400

1200

1000

800

600

400

crn -f
Figure 3
chabazite

I n f r a r e d r e f l e x t i o n spectra ( 2 0 0 - 1 4 0 0 cm -~) o f natural

o
200

400

600

800

1000

1200

1400

cm -I
Figure 4
Dispersion c u r v e o f t h e c o m p l e x r e f r a c t i v i t y i n d e x of
natural chabazite

334

ZEOLITES, 1983, Vol. 3, October

be spearated into three groups according to the

wavenumber range measured: (1) 3600-1400
cm -I - infrared absol'ption spectra in the medium
region and Raman spectra; (2) 1400-200 cm -1 infrared absorption spectra in the medium region,
part of the FIR spectra, reflectance spectra and
Raman spectra; (3) 2 0 0 - 4 0 cm -1 -- FIR spectra
and Raman spectra.
(1) Bands of the antisymmetric and symmetric
stretching vibrations of hydroxyl groups lie in the
region 3700-3420 cm -1. They have a very strong
intensity in the infrared spectra and low intensity
in the Raman scattering spectra. The shift of this
vibration relative to the wavenumber of the same
vibration for water vapour indicates the presence
of hydrogen bonds and intcratomic distance
O . - . O can be determined graphically for these
bonds 6. Combination libration braids of H20
can he found in the wavenumber region 24002 5 0 0 c m -1 in the infrared spectra, with bands of

Study of the complex vibrational spectra of natural zeolite -- chabazite: F. Pechar and O. Rykl

100

50

I
200

I
400

I
600

800

I
I000

I
1200

I
1400

I
1600

~1

I
3400

I
3600

cm "l
Figure

Raman scattering spectra ( 5 0 - 4 0 0 0 c m ~) of natural chabazite

Table 1 Chemical composition ofchabazite

Oxide

Mass (%)

SiO,

47.15

AI20 ~
Fe~O3
CaO
TiO 2
MnO
SrO
MgO
Na20
K20
"-2"H,O

19.62
0.15
8,85
0.05
0.01
0.66
0.18
1.54
1.13
20.19

"J

100.53

Group vibrational representation:

Gvib. = 22Alg(R) + 22A2g + 44Eg(R) + 2 2 A l u + 22A2u(i.r.)
+ 44E'u(i.r.).

low intensity. These bands have not been fotmd in

the Raman scattering spectra.
The H - O - H bending vibration lies at a wavcnumber
ira the region of 1610 cm -1 in the infrared absorption spectrum with m e d i u m intensity and at waven u m b e r of 1680 cm -~ in the Raman spectrum with
low intensity band.
(2) The infrared absorption spectrum, reflectivity
spectrum and Raman spectrum contain bands of
the antisymmetric stretching vibration of the tetrahedral Si(A1)-O bonds with a w a v e n u m b e r of
1 0 8 0 - 8 2 0 cm -1. These bands have high intensity
in the infrared spectra, medium in the reflectivity
spectra and Raman scattering spectra. All spectra
except ira the Far-infrared, contain bands with
varying intensity in the various spectra that can
be assigned to the symmetric stretching vibration
of the Si(A1)-O bonds. These bands lie at waven u m b e r 7 9 0 - 7 1 0 cm -l. The libration bands of the
water molecule around the a and c axes of this

molecule lic at 620 cm -l in infrared absorption

spectra with low intensity.
The bending vibration of the tetrahedral bonds
ct)rresponds to bands at a wavenumber in the range
of 4 2 0 - 4 0 0 cm -l. The external vibration of bonds
between the tetrahe(lra corresponds to bands at
wavenumber 1 2 1 0 - 1 1 1 0 cm -1 ira all the studied
spectra, except Far-infrared. These b~mds are of
varying intensity in the various spectra.
The translational modes of the crystal lattice
correspond to bands at wavenumbers 3 8 0 - 2 2 0
cm -I ira all the studied spectra. The bands of 'Pore
opening' vibration of oxygen rings of the framework chabazite c~m be f o u n d in all the spectra
except FIR in the wavenumber of 5 2 0 - 5 0 5 cm -1.
Bands of varying intensity, assigned to the Ca-O
vibration, can be f o u n d in the wavenumber region
of 2 9 0 - 2 6 0 c m -1.
(3) The bands of the translational mode of the
Na-O bonds can be f o u n d in the F I R and R spectra
in the wavenumber range 2 1 0 - 1 8 0 cm -1. The bands
with wavenumber lower than 180 cm -I can be
assigned to the vibrations of the cation-water
complexes and to the translational modes of the
K-O bonds or the chabazite cwstal lattice.
The theoretical frequencies of the vibrations of
the individual bonds or structural groups of
chabazite c o m p u t e d using the GCCC, LSMA and
BGLZ 1 programs, considering the simplifying
assumptions e m p l o y e d l, exhibit g o o d agreement
with the measured values and can be reliably used
to assign the measured peaks to the vibrations of
certain bonds or structural groups.
The dispersion curves of the crystal optical constants c o m p u t e d using the KKK-1 program have a

ZEOLITES, 1983, Vol. 3, October

335

Study of the complex vibrational spectra of natural zeolite - chabazite: F. Pechar and D. Rykl
Table 2

T a b l e 3 Force constants and theoretical frequencies o f chabazite

vibrations

Evaluation o f all the studied vibrational spectra of

chabazite
Type of spectrum
Type of
vibration

i.r.

3610-3490

2400 v w
1610 m
1 0 8 0 - 9 9 0 vs

3
4

780 v w
740 w

1110w

420 w
405 w
505 w

8
9
10

REF

Bond

3520 w
3480 w
3420 w

O-H
H-O-H

980-820 m

1680 v w
1080 w
1040 w
1010 rn
790 v w
740 v w
710 s
1210vw
1180w
400 w

420 m

420 v w

510 w

520 w
505 m

260 w
205 w
180 w
98 v w
82 v w
155 v w
140 m
110vw
370 w
360 m
330 w
220 w

290 v w
210 w

12

100 w
80 m

13
14
380 w
220 m

F~,
F,2
Ft3
F~.~

7.792
0.105
0.253
0.769

Libration
H20

K
K
KH
K0

0.230
0.130
0.172
0.451

Si-O

F~
F2
F3
F,
Fs
F~

6.310
6.420
6.894
4.975
3.289
3.060

F,
F:
F3
F~
Fs
F6

4.080
3.810
3.940
2.285
3.015
3.160

AI-O

620 w

11

15

FIR

110vw
230 w

O - A I - O

i.r. = infrared absorption spectra, FIR = far-infrared absorption

spectra, REF = infrared reflectance spectra, R = Raman scattering
spectra, vs = very strong band, s =strong, m = medium, w = weak,
v w = very weak band.
1 = a n d s y m m e t r i e and symmetric stretching vibration O - H
2 = c o m b i n a t i o n band H,O
3 = bending H - O - H
4 = antisymmetric stretching Si (AI)-O
5 = s y m m e t r i c stretching Si(AI)-O
6 = external TO,
7 = bending O - S i ( A I ) - O
8 = 'Pore opening' oxygen rings
9 = libration H20
10 = Ca-O
11 = N a - O
12 = Ca-H=O complex
13 = Na-H,O complex
14= K-O
15 = optical translational mode of lattice

similar m a x i m u m distribution as the reflectance

spectra in agreement with the theory 3.
CONCLUSION
Study of the complex vibrational spectra of
crystalline substances rapidly yields information
of the symmetry and dynamics of the crystal
lattice and on the dispersion of the optical
constants in the whole region of measured frequencies for individual types of electromagnetic
radiation. It also provides information on the
presence and strength of the individual types of
bonds in the crystal mad %n the mobility of water
or of the cations. It is thus an indispensable cornplement to X-ray or neutron diffraction in the
study of crystals.

336

Z E O L I T E & 1983, Vol. 3, October

Theoretical
frequencies
(cm -I)
3650
1650

625
590
481

1086
927
872

930
870
751

O-Si-O

380 w

Force constants
(X 10 -~ N m - ' )

AI-O-Si

O-O
Ca-O
Na-O
K-O

F L, 0.997
F~: 1.000
FL~ 0.994
F2~ 1.055
F~ 1.060
FL,
F~2
F~3
F, 3
F~3

1.135
1.145
1.138
1.216
1.222

F~
F,,
F,3
F2~
F,~

0.224
0.222
0.241
0.238
0.235

Fz~
F k~
F,~
FH

0.1187
0.0364
0.0175
0.0112

492
420
530

401
416
402

1150
1210

368
265
198
110

ACKNOWLEDGEMENTS
The authors wish to thank Dr. I. Gregora and
Dr. J. Petzelt and Dr. M. Zfiv0.tov5 at the Physical
Institute of the Czechoslovak Academy of
Sciences, Prague, for measuring the spectra.
REFERENCES
1
2
3
4
5
6

Schimanouchi, T. 'Computer program f o r normal coordinate

treatment of p o l y a t o m i c molecules', University of T o k y o , 1968
Petzelt, J. and Kroupa, P. 'Computer program for treatment
of Kramers-Kronig theorem', PI (~SAV Prague, 1979
Poulet, H. and Mathieu, J. P. 'Spectres de vibration et
sym~trie des cristaux', Gordon et Breach, Paris, 1973
Ross, S. D. 'Inorganic infrared and Raman spectra', McGrawHill, London, 1972
Turell, G. 'Infrared and Raman spectra of crystals', Academic
Press, London, 1972
Pechar, F . a n d Rykl, D. 'Infrared absorption spectra of natural
zeolites', Academia, Prague, in press