JOURNAL OF RAMAN SPECTROSCOPY

J. Raman Spectrosc. 2008; 39: 1250–1256

Published online 31 March 2008 in Wiley InterScience
(www.interscience.wiley.com) DOI: 10.1002/jrs.1978

Raman spectroscopy of hydroxy nickel carbonate

minerals nullaginite and zaratite
Ray L. Frost,∗ Marilla J. Dickfos and B. Jagannadha Reddy
Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, Brisbane Queensland
4001, Australia

Received 18 October 2007; Accepted 18 February 2008

Raman spectroscopy combined with infrared spectroscopy has been used to study the minerals, nullaginite
and zaratite. Raman bands are observed at 3650, 3556 and 3309 cm−1 for nullaginite and 3609, 3516 and
3336 cm−1 for zaratite. By using a Libowitzky-type empirical function, estimation of the hydrogen-bond
distances of the OH and water units has been made, which vary from 0.268 to 0.332 nm. Hydrogen-bond
distances of OH units are less than those for the water units. The observation of multiple asymmetric
stretching and bending modes for nullaginite suggests that the carbonate is strongly distorted in contrast
to zaratite for which only single bands are found. Raman bands at around 935 and 980 cm−1 are assigned
to OH deformation modes. Copyright  2008 John Wiley & Sons, Ltd.

KEYWORDS: nullaginite; zaratite; hellyerite; nickel carbonates; Raman spectroscopy

INTRODUCTION
In nature there exist two hydroxy nickel carbonate
minerals nullaginite Ni2
CO3 
OH2 1 – 3 and zaratite
ž used to investigate carbonates.16,19 – 25 A detailed single-
Ni3
CO3 
OH4 4
H2 O.4 – 8 Other non-mixed cationic
ž crystal Raman study of selected mineral carbonates has
nickel carbonates include hellyerite NiCO3 6H2 O,9
ž
widgiemoolthalite Ni5
CO3 4
OH2 5H2 O10 and otwayite
ž
Ni2 CO3
OH2 H2 O.11 There are a significant number of
nickel carbonates with mixed cations, especially with
a layered double hydroxide structure, which include
carboydite, comblainite, mountkeithite, reevesite and
takovite.12 – 18 Nullaginite is monoclinic with point group 2/m
and is a member of the rosasite mineral group. Nullaginite
is formed in the oxidised zone of nickel-rich hydrothermal
ore deposits. Zaratite is of an unknown structure and is
an uncommon secondary mineral formed by alteration of
chromite, pentlandite, pyrrhotite and millerite in ultramafic
rocks.
It is important to study the gaspeite–hellyerite–null-
aginite assemblage and the relative stability of the minerals.
The reason is that these minerals are the stable minerals
at atmospheric pressure. Such minerals may be used as a
sink for carbon dioxide. Therefore, these minerals could be
of importance for the geosequestration of greenhouse gases.
Pumping liquid CO2 below the ground where suitable nickel
deposits are found could result in the formation of nullaginite
Ł Correspondence to: Ray L. Frost, Inorganic Materials Research
Program, School of Physical and Chemical Sciences, Queensland
University of Technology, Brisbane Queensland 4001, Australia.
E-mail: r.frost@qut.edu.au
and zaratite. One important method for the analysis of nickel-
bearing carbonate minerals is to use vibrational spectroscopic
techniques. Infrared and Raman spectroscopies have been
been undertaken.19,24 The application of Raman spectroscopy
would seem to be an important tool for their determination
in the context of the stability of the hydroxy carbonates of
Ni, Zn, Cu and Pb. However, the vibrational spectroscopy
of many carbonates of Ni has not been reported. This
may be due to the unknown structure of some nickel
hydroxy carbonates. A few infrared spectral studies of
related minerals such as the rosasite group have been
forthcoming.25 – 28 The observation of two bands for malachite
suggests coupling of the hydroxyl stretching vibrations.19
This coupling was not observed for azurite.19 Malachite has a
characteristic infrared active intense band at ¾430 cm
1 , and
for azurite an intense band at ¾400 cm
1 . The deformation
modes of azurite were reported at 1035 and 952 cm
1
and at 1045 and 875 cm
1 for malachite.25,29 Minerals in
the rosasite group, of which nullaginite is a member,
(a group of copper hydroxy carbonates) namely, rosasite,
glaukosphaerite, kolwezite, mcguinnessite, nullaginite and
pokrovskite, have been studied by Raman spectroscopy at
298 and 77 K.22,30
Vibrational spectroscopic studies of carbonate miner-
als have been undertaken over an extended period of
time.31 – 33 Adler and Kerr31 showed that differences in the
infrared absorption spectra of carbonates were a function

Copyright  2008 John Wiley & Sons, Ltd.


of cation size. Raman studies also have been forthcom-
ing but not recently.34 – 36 Farmer37 reported the vibrational
wavenumbers of calcite-structured minerals (Table 12. IX
page 239). In this table, the band positions for smithsonite
were listed as 1093 cm
1 (1 symmetric stretching mode),
1412 and 1440 cm
1 (3 antisymmetric stretching mode),
870 cm
1 (2 in-plane bending mode), 733 and 743 cm
1 (4
out-of-plane bending mode) with lattice modes at 307, 200,
165 cm
1 . This table reported the results of the infrared
spectrum of gaspeite.38 Some variation of band positions is
found in the literature. Very little spectroscopic information
on carbonates including hydrated and hydroxyl carbon-
ates of nickel is available. However, a comparison may be
made with the mineral aurichalcite. The mineral aurichalcite

Zn,Cu2C 5
CO3 2
OH6 is also monoclinic as are many of
the other hydroxy carbonates such as malachite.39 – 41 The
accurate X-ray crystallography of zaratite and nullaginite
is difficult to obtain because of its very small interwoven
needles, which makes single-crystal studies difficult or less
reliable.41 – 44 Reports regarding the chemical analysis, ESR,
electronic and some limited infrared spectroscopic studies
have been published.45 These works reported optical spec-
tra revealing the presence of copper in D4h symmetry with
crystal field (Dq) and tetragonal field (Ds and Dt). This
research was further extended to a comparison of rosasite
and aurichalcite.46 Optical and EPR spectra of aurichalcite
accounted for Cu2C ion in the distorted octahedron site.46
Stoilova et al.47 (2002) reported the infrared spectra of a
series of synthetic hydroxy carbonates containing Cu2C .
Raman spectroscopy has proven very useful for the
study of minerals.48 – 50 Indeed, Raman spectroscopy has
proven most useful for the study of diagentically related
minerals such as zaratite and nullaginite as often occurs with
carbonate minerals.51 – 55 Some previous studies have been
undertaken by the authors using Raman spectroscopy to
study complex secondary minerals formed by crystallisation
from concentrated sulfate solutions.56 Few Raman studies of
any note are available.57,58 The aim of this paper is to present
Raman and infrared spectra of the zaratite and nullaginite
and to relate the Raman spectra to the structure of the
mineral.
The paper is a part of systematic studies of the vibrational
spectra of minerals of secondary origin in the oxide
supergene zone and their synthetic analogues. In this paper
we report the Raman and infrared spectra of nullaginite and
zaratite.
EXPERIMENTAL
Minerals
The minerals were obtained from CSIRO, Western Australia.
The minerals were loaned through the courtesy of Dr Ernie
Nickel. These minerals have already been characterised.1 – 3
The samples were phase-analysed by X-ray diffraction and
measured for chemical composition by EDX.
Copyright  2008 John Wiley & Sons, Ltd.
Raman spectra of nullaginite and zaratite 1251
Raman microprobe spectroscopy
The crystals of nickel hydroxy carbonates were placed and
oriented on the stage of an Olympus BHSM microscope,
equipped with 10ð and 50ð objectives and part of a
Renishaw 1000 Raman microscope system, which also
includes a monochromator, a filter system and a charge-
coupled device (CCD). Raman spectra were excited by a
He–Ne laser (632.8 nm) at a nominal resolution of 2 cm
1 in
the range between 100 and 4000 cm
1 . Repeated acquisition
using the highest magnification was made to improve
the signal-to-noise ratio. Spectra were calibrated using the
520.5 cm
1 line of a silicon wafer. Details of the technique
have been published by the authors.21,59 – 61
Mid-IR spectroscopy
Infrared spectra were obtained using a Nicolet Nexus 870
FTIR spectrometer with a smart endurance single bounce
diamond attenuated total reflection (ATR) cell. Spectra over
the 4000–525 cm
1 range were obtained by the co-addition
of 64 scans with a resolution of 4 cm
1 and a mirror velocity
of 0.6329 cm/s. Spectra were co-added to improve the signal-
to-noise ratio.
Spectral manipulations such as baseline adjustment,
smoothing and normalisation were performed using the
Spectracalc software package GRAMS (Galactic Industries
Corporation, NH, USA). Band component analysis was
undertaken using the Jandel ‘Peakfit’ software package,
which enabled the type of fitting function to be selected and
allows specific parameters to be fixed or varied accordingly.
Band fitting was done using a Lorentz–Gauss cross-product
function with the minimum number of component bands
used for the fitting process. The Gauss–Lorentz ratio was
maintained at values greater than 0.7 and fitting was
undertaken until reproducible results were obtained with
squared correlations of r2 greater than 0.995.
RESULTS AND DISCUSSION
Spectroscopy of carbonate anion
Nakamoto et al.62 first published and tabulated the selec-
tion rules for unidentate and bidentate anions including
the carbonate anion. The free ion, CO3 2
with D3h symme-
try exhibits four normal vibrational modes: a symmetric
stretching vibration (1 ), an out-of-plane bend (2 ), a dou-
bly degenerate asymmetric stretch (3 ) and another doubly
degenerate bending mode (4 ). The symmetries of these
modes are A1 0
R C A2 00
IR C E0
R, IR C E00 (R, IR), and
occur at 1063, 879, 1415 and 680 cm
1 , respectively. Gener-
ally, strong Raman modes appear around 1100 cm
1 owing
to the symmetric stretching vibration (1 ) of the carbon-
ate groups, while intense IR and weak Raman peaks near
1400 cm
1 are due to the asymmetric stretch (3 ). Infrared
modes near 800 cm
1 are derived from the out-of-plane bend
(2 ). Infrared and Raman modes around 700 cm
1 region are
due to the in-plane bending mode (4 ). This mode is doubly
J. Raman Spectrosc. 2008; 39: 1250–1256
DOI: 10.1002/jrs
1252 R. L. Frost, M. J. Dickfos and B. Jagannadha Reddy

degenerate for undistorted CO3 2
groups.62 As the carbon-

ate groups become distorted from regular planar symmetry,
this mode splits into two components.62 Infrared and Raman
spectroscopies provide sensitive test for structural distortion
of CO3 2
.
The Raman spectra of nullaginite and zaratite in the
2600 to 3800 cm
1 region are shown in Fig. 1. The Raman
spectrum of nullaginite suffers from a lack of quality because
of an intense fluorescent background. Such fluorescence may
indicate the incorporation of actinide and or lanthanide
cations in the nullaginite. Deconvolution of such a spectrum
must be treated with caution. Raman bands in this spectral
region of nullaginite are observed at 3309, 3556 and
3650 cm
1 . These bands are attributed to OH stretching
vibrations. In the infrared spectrum in the 2500 to 3800 cm
cm
1 region (Fig. 2), two intense sharp bands are observed
at 3645 and 3681 cm
1 with broader bands observed at 3269,
3473 and 3602 cm
1 . The first two bands of nullaginite are
ascribed to the OH stretching vibrations of nullaginite and
the latter three bands to the water stretching vibrations.

Figure 2. Infrared spectra of nullaginite and zaratite in the 2500

to 3800 cm
1 region.

In the Raman spectrum of zaratite (Fig. 2), two sets of

Figure 1. Raman spectra of nullaginite and zaratite in the 2600
to 3800 cm
1 region.
bands are displayed: (1) bands at 3336, 3516 and 3609 cm
1
and (2) bands at 2751, 2867, 2933 and 2981 cm
1 . It is probable
that these latter four bands are due to the presence of organic
molecules on the mineral surface. The first three bands are
attributed to OH stretching vibrations. In the infrared spectra
of zaratite, two sharp, intense bands in similar position to that
of nullaginite are found at 3648 and 3686 cm
1 . The broad
infrared bands at 3097, 3380 and 3569 cm
1 are assigned to
water stretching vibrations. The bands at 2854 and 2924 cm
1
are as in the Raman spectrum assigned to CH stretching
bands due to adsorbed organic molecules.
Studies have shown a strong correlation between OH
stretching wavenumbers and both OÐ Ð ÐO bond distances and
HÐ Ð ÐO hydrogen bond distances.63 – 66 Libowitzky67 showed
that a regression function can be employed relating the
hydroxyl stretching frequencies with regression coefficients
better than 0.96 using infrared spectroscopy. The func-

d
O
O
tion is described as: 1 D
3592
304 ð 109 0.1321 cm
1 .

Copyright  2008 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2008; 39: 1250–1256
DOI: 10.1002/jrs
 Raman spectra of nullaginite and zaratite 1253

Thus OHÐ Ð ÐO hydrogen bond distances may be calcu-

lated using the Libowitzky empirical function. The val-
ues for the OH stretching vibrations delineated above
provide hydrogen-bond distances for nullaginite based
on the Raman wavenumbers of 0.275 nm
3309 cm
1 ,
0.319 nm
3556 cm
1 , 0.320 nm
3650 cm
1 . Estimation
of hydrogen-bond distances for nullaginite based on
infrared wavenumbers are 0.273 nm
3269 cm
1 , 0.286 nm

3473 cm
1 , 0.310 nm
3602 cm
1 , 0.320
3645 cm
1  and
0.330
3681 cm
1 . The values for the OH stretching
vibrations delineated above provide hydrogen-bond dis-
tances for zaratite based on the Raman wavenumbers
of 0.291 nm
3516 cm
1  and 0.315 nm
3609 cm
1 . Esti-
mation of hydrogen-bond distances for zaratite based on
infrared wavenumbers are 0.268 nm
3097 cm
1 , 0.278 nm

3380 cm
1 , 0.307 nm
3569 cm
1 , 0.320 nm
3648 cm
1 
and 0.332 nm
3686 cm
1 . It is noted that such hydrogen-
bond distances as listed in Table 1 are not easily determined
and cannot be determined by single-crystal X-ray diffraction
techniques. Some conclusions may be drawn from these cal-
culations. First, the hydrogen-bond distances of OH units
attributed to water are significantly shorter than those of OH
units. This suggests the the water molecules are hydrogen-
bonded to the carbonate units. Second, the hydrogen bonding
of OH units to carbonate units is weaker as determined by the
H-bond distances. By using Libowitzky-type empirical rela-
tionships, estimates of the hydrogen-bond distances can be
made. Such determinations are difficult to make otherwise.
The Raman spectra in the 800 to 2200 cm
1 region of
nullaginite and zaratite are shown in Fig. 3. The Raman
spectrum of zaratite appears simpler than that of nullaginite.
The bands at 1072 cm
1 are assigned to the
CO3 2
1
symmetric and 3 antisymmetric stretching modes of the Figure 3. Raman spectra of nullaginite and zaratite in the 800
carbonate anion. The band at 1612 cm
1 is attributed to to 2200 cm
1 region.
the water bending mode. The position of this band shows
that the water is only weakly bonded. The bands at antisymmetric stretching vibrations. The Raman band at
935 and 980 cm
1 are assigned to water OH deformation 1639 cm
1 may be assigned to water bending modes even
modes. The band at 2115 cm
1 is assigned to an overtone. though the intensity of the water bending mode is often of
For nullaginite, the band at 1094 cm
1 is assigned to the very low intensity in the Raman spectrum. When significant

CO3 2
1 symmetric stretching vibration. Two bands intensity is observed, it indicates that the water is in a
for nullaginite at 1430 and 1546 cm
1 are ascribed to position of high symmetry. The mineral does not have

CO3 2
3 antisymmetric stretching vibrations. A single water units in its molecular formula, and therefore the
band at 1367 cm
1 for zaratite is assigned to the
CO3 2
3 band must be attributed to adsorbed water. The band at

Table 1. Estimation of hydrogen-bond distances of OH units and water molecules

Nullaginite Zaratite
Raman H-bond distance Infrared H-bond distance Raman H-bond distance Infrared H-bond distance
(cm
1 ) (nm) (cm
1 ) (nm) (cm
1 ) (nm) (cm
1 ) (nm)

3309 0.275 3269 0.273 3516 0.291 3097 0.268

3556 0.319 3473 0.286 3609 0.315 3380 0.278
3650 0.320 3602 0.310 – – 3569 0.307
– – 3645 0.320 – – 3648 0.320
– – 3681 0.330 – – 3686 0.332

Copyright  2008 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2008; 39: 1250–1256
DOI: 10.1002/jrs
1254 R. L. Frost, M. J. Dickfos and B. Jagannadha Reddy
927 cm
1 is, as for zaratite, assigned to OH deformation
vibrations.
The infrared spectra in the 550 to 1750 cm
1 region of
nullaginite and zaratite are shown in Fig. 4. The infrared
spectrum is limited to the cut-off point at 550 cm
1 at which
point the diamond ATR cell starts absorbing the infrared
radiation. However, such a cut-off point does not affect the
infrared spectroscopy of minerals containing carbonate, as
all the bands are above 550 cm
1 . The infrared spectrum of
nullaginite is dominated by the intense band at 934 cm
1 .
This band is assigned to the OH deformation vibration. This
band is observed at 941 cm
1 for zaratite. The shoulder at
1070 cm
1 is the infrared equivalent of the Raman band
observed at 1094 cm
1 . This band is found at 1072 cm
1 for
zaratite. The second most intense band is at 617 cm
1 and
is attributed to the 4 bending mode. This infrared band
is observed at 584 cm
1 for zaratite. The band at 806 cm
1
for nullaginite and at 832 cm
1 for zaratite is assigned to
the 2 bending mode. Interestingly, Farmer37 reported part
of the infrared spectrum of zaratite. He reported 2 bands
Figure 4. Infrared spectra of nullaginite and zaratite in the 550
to 1750 cm
1 region.
Copyright  2008 John Wiley & Sons, Ltd.
at 881 and 835 cm
1 . In this work, we could not identify
a band at 881 cm
1 as the band is within the spectral
profile of the 934 cm
1 band. The infrared bands at 1070
and 1072 cm
1 for nullaginite and zaratite are assigned to the
(so-called infrared forbidden) 1 symmetric stretching mode.
A complex infrared spectral profile for zaratite is observed
at around 1350 cm
1 with resolvable component bands at
1324, 1345 and 1386 cm
1 . These bands may be ascribed to
the
CO3 2
3 antisymmetric stretching vibrations. Multiple
bands provide an indication of the distortion of the
CO3 2

anion in the zaratite structure. Only a low-intensity band at
1371 cm
1 is observed for nullaginite.
A comparison may be made with the spectra of other
carbonate minerals such as rosasite of which nullaginite has a
similar structure.22,30,68 The infrared spectrum of the mineral
rosasite shows two intense bands at 870 and 818 cm
1 .
These bands are assigned to the 2 bending modes of the

CO3 2
units. The first band is not Raman active, as is
observed by the absence of any intensity. A Raman band
for rosasite is observed at 817 cm
1 , which corresponds to
Figure 5. Raman spectra of nullaginite and zaratite in the 100
to 800 cm
1 region.
J. Raman Spectrosc. 2008; 39: 1250–1256
DOI: 10.1002/jrs

the infrared band at 818 cm
1 . The observation of two 2
bands is in harmony with the observation of two sets of
bands in the 3 antisymmetric stretching region. The infrared
spectrum of malachite shows two bands at 820 and 803 cm
1
ascribed to
CO3 2
2 bending modes as does azurite at 837
and 817 cm
1 . Hydrocerrusite infrared spectrum shows two
bands at 850 and 834 cm
1 . For rosasite, infrared bands are
observed at 776, 748 and 710 cm
1 . These bands are assigned
to the 4
CO3 2
bending modes. In the Raman spectrum,
bands are observed at 751 and 719 cm
1 . For malachite, two
infrared bands are observed at 748 and 710 cm
1 , which are
assigned to this 4
CO3 2
bending vibration.
The Raman spectrum of the low wavenumber region of
nullaginite and zaratite are shown in Fig. 5. The band at 683
and 777 cm
1 for nullaginite and zaratite may be assigned
to the 4 bending mode. The intense band at 144 cm
1 for
nullaginite may be attributed to O–Ni–O bending modes. A
band at 145 cm
1 is observed for zaratite, which is attributed
to the same mode. A band at 453 cm
1 for zaratite may be
assigned to the NiO stretching vibration.
CONCLUSIONS
The understanding of the thermal stability of nickel carbon-
ates and the relative stability of hydrous and hydrated nickel
carbonates including zaratite and nullaginite is extremely
important to the geosequestration process for the removal of
atmospheric CO2 . The hydration–carbonation or hydration-
and-carbonation reaction path in the NiO–CO2 –H2 O and
NiS–CO2 –H2 O systems at ambient temperature and atmo-
spheric CO2 is of environmental significance from the stand-
point of carbon balance and the removal of greenhouse gases
from the atmosphere. If CO2 with air is pumped into ore
bodies containing NiO or NiS, it is probable that a range of
carbonate minerals of Ni will be formed. One method for
the study of nickel carbonate minerals is to use vibrational
spectroscopy.
The Raman spectra of nullaginite and zaratite show
intense sharp bands at 1072 and 1094 cm
1 and are assigned
to the
CO3 2
1 symmetric stretching mode. Raman
bands for nullaginite and zaratite observed at 1430 and
1546 cm
1 and at 1367 cm
1 are assigned to the 3
CO3 2

antisymmetric stretching modes. In the infrared spectra,
the intense bands at 934 and 941 cm
1 for nullaginite and
zaratite are attributed to the OH deformation vibration.
For nullaginite and zaratite, the Raman bands at 683 and
777 cm
1 are attributed to the 4 in-phase bending mode. In
the infrared spectra, the intense bands at 617 and ¾584 cm
1
are observed for nullaginite and zaratite, respectively, and
are also assigned to the
CO3 2
4 in-phase bending modes.
Low-intensity bands at 806 cm
1 (nullaginite) and 832 cm
1
(zaratite) are ascribed to the 2 mode.
Acknowledgements
The financial and infra-structure support of the Queensland
University of Technology, Inorganic Materials Research Program, is
Copyright  2008 John Wiley & Sons, Ltd.
Raman spectra of nullaginite and zaratite 1255
gratefully acknowledged. The Australian Research Council (ARC)
is thanked for funding the instrumentation.
REFERENCES
1. Nickel EH, Berry LG. Can. Mineral. 1981; 19: 315.
2. Nickel EH, Clout JFM, Gartrell BJ. Mineral. Rec. 1994; 25: 283.
3. Nickel EH, Hallbert JA, Halligan R. J. Geol. Soc. Aust. 1979; 26:
61.
4. Fenoglio M. Period. Mineral. 1934; 5: 33.
5. Haupt J. Mineral. Rec. 1988; 19: 381.
6. Isaacs T. Mineral. Mag. 1963; 33: 663.
7. Pelloux A. Period. Mineral. 1931; 2: 44.
8. Pelloux A. Neues Jahrb. Mineral. Geol. 1932; 228.
9. Williams KL, Threadgold IM, Hounslow AW. Am. Mineral. 1959;
44: 533.
10. Nickel EH, Robinson BW, Mumme WG. Am. Mineral. 1993; 78:
819.
11. Frost RL, Weier ML, Martens WN, Mills SJ. Neues Jahrb. Mineral.,
Abh. 2006; 183: 107.
12. Frost RL, Adebajo MO, Erickson KL. Spectrochim. Acta, Part A:
Mol. Biomol. Spectrosc. 2005; 61: 613.
13. Frost RL, Erickson KL. Spectrochim. Acta, Part A: Mol. Biomol.
Spectrosc. 2004; 61A: 51.
14. Frost RL, Weier ML, Clissold ME, Williams PA. Spectrochim.
Acta, Part A: Mol. Biomol. Spectrosc. 2003; 59: 3313.
15. Frost RL, Weier ML, Clissold ME, Williams PA, Kloprogge JT.
Thermochim. Acta 2003; 407: 1.
16. Frost RL, Weier ML, Kloprogge JT. J. Raman Spectrosc. 2003; 34:
760.
17. Lin Y-H, Adebajo MO, Frost RL, Kloprogge JT. J. Therm. Anal.
Calorim. 2005; 81: 83.
18. Lin Y-H, Adebajo MO, Kloprogge JT, Martens WN, Frost RL.
Mater. Chem. Phys. 2006; 100: 174.
19. Frost RL, Martens WN, Rintoul L, Mahmutagic E, Kloprogge JT.
J. Raman Spectrosc. 2002; 33: 252.
20. Johnson TE, Martens W, Frost RL, Ding Z, Kloprogge JT.
J. Raman Spectrosc. 2002; 33: 604.
21. Frost RL, Henry DA, Erickson K. J. Raman Spectrosc. 2004; 35:
255.
22. Frost RL. J. Raman Spectrosc. 2006; 37: 910.
23. Frost RL, Bouzaid JM. J. Raman Spectrosc. 2007; 38: 873.
24. Goldsmith JA, Ross SD. Spectrochim. Acta, Part A: Mol. Biomol.
Spectrosc. 1968; 24: 2131.
25. Rodriguez PC. Bol. Soc. Quim. Peru 1969; 35: 38.
26. Wada K. Kan. Ch. Buns. 1978; 19: 133.
27. Tarte P. Investigation of the OH deformation frequency. The
infrared spectrum of malachite [CuCO3 Ð Cu
OH2 ]. Proceedings
of the 4th International Meeting on Molecular Spectroscopy, 1959,
vol. 3, Bologna, 1962; 1041.
28. Tarte P, Deliens M. Bull. Soc. R. Sci. Liege 1974; 43: 96.
29. Rocchiccioli C. C. R. 1964; 259: 4581.
30. Frost RL, Wain DL, Martens WN, Reddy BJ. Polyhedron 2007; 26:
275.
31. Adler HH, Kerr PF. Am. Mineral. 1963; 48: 124.
32. Huang CK, Kerr PF. Am. Mineral. 1960; 45: 311.
33. Moenke H, Zabinski W. Geologie (Berlin) 1963; 12: 1221.
34. Griffith WP. Nature (London, United Kingdom) 1969; 224: 264.
35. Herman RG, Bogdan CE, Sommer AJ. Mater. Sci. Res. 1985; 19:
113.
36. Griffith WP. J. Chem. Soc. A 1970; 286.
37. Farmer VC. Mineralogical Society Monograph 4: The Infrared Spectra
of Minerals, 1974.
38. Reddy BJ, Frost RL. Neues Jahrb. Mineral., Monatsh. 2004; 525.
39. Braithwaite RS, Ryback G. Mineral. Mag. 1963; 33: 441.
J. Raman Spectrosc. 2008; 39: 1250–1256
DOI: 10.1002/jrs
1256 R. L. Frost, M. J. Dickfos and B. Jagannadha Reddy
40. Herman RG, Bogdan CE, Kumler PL, Nuszkowski DM. Mater.
Chem. Phys. 1993; 35: 233.
41. Jambor JL. Can. Mineral. 1964; 8: 92.
42. Jambor JL, MacGregor ID. Pap. – Geol. Surv. Can. 1974; 74-1(Pt.
B): 172.
43. Anthony JW, Bideaux RA, Bladh KW, Nichols MC. Handbook of
Mineralogy, vol. 5, Mineral Data Publishing: Tiscon, 2003.
44. Harding MM, Kariuki BM, Cernik R, Cressey G. Acta
Crystallogr., Sect. B: Struct. Sci. 1994; B50: 673.
45. Vedanand S, Sudhana BM, Reddy BJ, Rao PS. Bull. Mater. Sci.
1996; 19: 1089.
46. Reddy BJ, Nieto F, Navas AS. Neues Jahrb. Mineral., Monatsh.
2004: 302.
47. Stoilova D, Koleva V, Vassileva V. Spectrochim. Acta, Part A: Mol.
Biomol. Spectrosc. 2002; 58A: 2051.
48. Frost RL, Palmer SJ, Bouzaid JM, Reddy BJ. J. Raman Spectrosc.
2007; 38: 68.
49. Frost RL, Henry DA, Weier ML, Martens W. J. Raman Spectrosc.
2006; 37: 722.
50. Frost RL, Musumeci AW, Kloprogge JT, Adebajo MO,
Martens WN. J. Raman Spectrosc. 2006; 37: 733.
51. Frost RL, Cejka J, Weier M, Martens WN. J. Raman Spectrosc.
2006; 37: 879.
52. Frost RL, Weier ML, Cejka J, Kloprogge JT. J. Raman Spectrosc.
2006; 37: 585.
53. Frost RL, Cejka J, Weier ML, Martens W. J. Raman Spectrosc. 2006;
37: 538.
Copyright  2008 John Wiley & Sons, Ltd.
54. Frost RL, Weier ML, Reddy BJ, Cejka J. J. Raman Spectrosc. 2006;
37: 816.
55. Frost RL, Weier ML, Martens WN, Kloprogge JT, Kristof J.
J. Raman Spectrosc. 2005; 36: 797.
56. Frost RL, Wills R-A, Weier ML, Martens W. J. Raman Spectrosc.
2005; 36: 435.
57. Fan H, Tao K, Xie Y, Wang K. Yan. Xue. 2003; 19: 169.
58. Hong W, He S, Huang S, Wang Y, Hou H, Zhu X. Guan. Guan.
Fen. 1999; 19: 546.
59. Frost RL. Spectrochim. Acta, Part A: Mol. Biomol. Spectrosc. 2004;
60A: 1469.
60. Frost RL, Carmody O, Erickson KL, Weier ML, Cejka J. J. Mol.
Struct. 2004; 703: 47.
61. Frost RL, Carmody O, Erickson KL, Weier ML, Henry DO,
Cejka J. J. Mol. Struct. 2004; 733: 203.
62. Nakamoto K, Fujita J, Tanaka S, Kobayashi M. J. Am. Chem. Soc.
1957; 79: 4904.
63. Emsley J. Chem. Soc. Rev. 1980; 9: 91.
64. Lutz H. Struct. Bond. (Berlin, Germany) 1995; 82: 85.
65. Mikenda W. J. Mol. Struct. 1986; 147: 1.
66. Novak A. Struct. Bond. (Berlin) 1974; 18: 177.
67. Libowitzky E. Monatsh. Chem. 1999; 130: 1047.
68. Frost RL, Wain DL, Martens WN, Reddy BJ. Spectrochim. Acta,
Part A: Mol. Biomol. Spectrosc. 2007; 66: 1068.
J. Raman Spectrosc. 2008; 39: 1250–1256
DOI: 10.1002/jrs