ORIGINAL PAPER

M. Prencipe F. Pascale C. M. Zicovich-Wilson

V. R. Saunders R. Orlando R. Dovesi
The vibrational spectrum of calcite (CaCO
3
): an ab initio
quantum-mechanical calculation
Received: 26 April 2004 / Accepted: 9 July 2004
Abstract The vibrational spectrum of calcite (CaCO
3
) is
evaluated at an ab initio periodic quantum-mechanical
level by using the CRYSTAL package. A localized basis
set of Gaussian-type functions and the B3LYP hybrid
Hamiltonian are adopted. The dynamical matrix is
obtained by dierentiating numerically the analytical
rst derivatives of the energy. The accuracy with respect
to all computational parameters is documented. The
calculated frequencies are compared with available IR
and RAMAN data (16 and 5 peaks, respectively), the
mean absolute error being less than 12 cm
1
(frequencies
range from 100 to 1600 cm
1
). Overall, the agreement
with experiment is very satisfactory, and shows that
simulation can produce at a relatively low cost the full
spectra of crystalline compounds of mineralogical
interest.
Keywords Vibrational spectroscopy
Quantum-mechanical calculations Calcite
Introduction
The calculation of vibrational spectra of molecular sys-
tems is a well-known procedure, implemented in several
relevant computer codes (Schmidt et al. 1993; Frisch
et al. 2001). The method is based on the calculation of
the Hessian matrix, either numerically or analytically,
although the latter option is a very demanding compu-
tational task (Stanton 1991). The situation is dierent
for innite periodic systems, where the development of
reliable and accurate computer codes is at an earlier
stage than in molecular quantum chemistry and only few
ab initio codes permit the calculation of vibrational
spectra of crystalline compounds.
The implementation in the periodic ab initio CRYS-
TAL code (Saunders et al. 2003), that uses a basis of
localized functions, is similar to the computational
scheme of molecular codes. It is based on the calculation
of analytical energy gradients with respect to the nuclear
positions (Doll et al. 2001; Doll 2001). The Hessian
matrix is then obtained by numerical dierentiation.
In a previous paper (Pascale et al. 2004) devoted to
the presentation of the method, the eect of the com-
putational parameters controlling the accuracy of the
calculated vibrational frequencies is discussed at length
with reference to a-quartz.
In the present paper such a scheme is used to calculate
the full vibrational spectrum of calcite CaCO
3
at the C
point; this permits a careful comparison with the available
IR and RAMAN spectra (Hellwege et al. 1970).
Calcite is an important polymorph of CaCO
3
. Its
structure [rombohedral, space group R3c, with two for-
mula units (Z) per cell, but often described in a hexag-
onal cell with Z 6] consists of a stacking of planar
CO
2
3
groups and Ca
2
ions along the c axis of the
hexagonal cell. Its structural and elastic properties have
Phys Chem Minerals (2004) 31: 559564 Springer-Verlag 2004
DOI 10.1007/s00269-004-0418-7
M. Prencipe (&)
Dipartimento di Scienze Mineralogiche e Petrologiche,
Universita` di Torino, Via Valperga Caluso 35,
10125 Torino, Italy
E-mail: mauro.prencipe@unito.it
Tel.: +390116705131
Fax: +390116705128
F. Pascale
Laboratoire de Cristallographie et Mode lisation des Mate riaux
Mine raux et Biologiques (LCM3B), UMR 7036,
Groupe Biocristallographie, Universite Henri Poincare , Nancy I,
Faculte des Sciences, BP 239, 54506 Vandoeuvre le` s Nancy
CEDEX, France
C. M. Zicovich-Wilson
Departamento de F sica, Universidad Auto noma del Estado de
Morelos, Av. Universidad 1001, Col. Chamilpa,
62210 Cuernavaca (Morelos), Mexico
V. R. Saunders R. Dovesi
Dipartimento di Chimica IFM, Universita` di Torino,
Via P. Giuria 7, 10125 Torino, Italy
R. Orlando
Dipartimento di Scienze e Tecnologie Avanzate,
Universita` del Piemonte Orientale, C.so Borsalino 54,
15100 Alessandria, Italy
been investigated in the past by using either quantum-
mechanical ab initio calculations (Catti and Pavese
1997) or model potentials (Dove et al. 1992; Pavese et al.
1992; Catti et al. 1993a; Catti and Pavese 1997; Pilati et
al. 1998). In particular, by using a previous version of
CRYSTAL, Catti and Pavese (1997) were able to obtain
the frequency of the A
1g
CO stretching mode within the
HartreeFock approximation. To date, however, no
quantum-mechanical calculations of the whole vibra-
tional spectrum of calcite have been performed, to the
authors knowledge.
The structure of the paper is as follows. We rst
summarize briey the method employed for the calcu-
lation of vibrational spectra; the stability of the calcu-
lated frequencies with respect to some of the
computational parameters will be checked, in order to
verify if the experience (very limited, so far) gained with
a semicovalent system like a-quartz (Pascale et al. 2004)
can be transferred as such to the present system, that has
a dierent structure and symmetry, and contains a
covalent part and a fully ionic part. The Results section
presents our calculated data and analyzes the vibrational
modes.
Computational details
Geometry optimization and spectra calculations were performed by
means of a development version of the ab initio CRYSTAL code
(Saunders et al. 2003), which implements the HartreeFock and
KohnSham, self consistent eld (SCF) method for the study of
periodic systems (Pisani et al. 1988).
Basis set
The multielectronic wave function is constructed as an anti-
symmetrized product (Slater determinant) of monoelectronic
crystalline orbitals (CO) that are linear combinations of local
functions (to be indicated as AOs) centred on each atom of the
crystal. In turn, AOs are linear combinations of Gaussian-type
functions (GTF, the product of a Gaussian times a real solid
spherical harmonic to give s, p and d-type AOs). In the
present case, calcium is described with a 86-511d3G basis (see
the CRYSTAL Web page
1
). It consists of eight and six con-
tracted GTFs for the description of the 1s and 2sp shells,
respectively; contractions of 5, 1 and 1 GTFs are respectively
used for the valence sp shells; the symbol d3 refers to the
presence of a contraction of three d GTFs. The exponents of the
two outer sp GTFs have been reoptimized in the present case
(0.453 and 0.295 bohr
2
, respectively). C and O are described by
6-21G* and 8-411G* basis sets, respectively (CRYSTAL page
1
;
see also Catti et al. 1993b, 1994; the star indicates the presence
of a d shell). The reoptimized exponents of the outer sp GTFs
(one for C and 2 for O) are 0.230, 0.486 and 0.1925 bohr
2
,
respectively. The exponents of the d GTFs for C and O are 0.8
and 0.5 bohr
2
, respectively.
Hamiltonian and computational parameters
The B3LYP Hamiltonian has been used, which contains a hybrid
HartreeFock/density-functional exchange-correlation term; such
a Hamiltonian is widely and successfully used in molecular
quantum chemistry (Koch and Holthausen 2000) as well as for
solid-state calculations. The exchange-correlation contribution is
evaluated numerically by integrating, over the cell volume (V
cell
), a
function f r of the electron density and its gradient. The choice of
the grid of points for the integration is based on an atomic partition
method, originally developed by Becke (1988) for molecular
systems and then extended to periodic systems. In this scheme, the
integration domain V
cell
of the function f r is partitioned into
atomic volumes, each centred at nucleus A and associated with
weight x
A
r. Spherical coordinates are introduced to separate
radial and angular integration
Z
Vcell
f rdr
X
A
Z
1
0
dr
A
r
2
A
Z
4p
0
dX x
A
r
A
; X
A
f r
A
; X
A

X
A
X
i;j
r
2
Ai
xr
Ai
; X
Aj
f r
Ai
; X
Aj
;
where the A sum extends to all the nuclei in the zero cell,
r
A
jr R
A
j is the distance of a point in the cell from nucleus A
and X is the solid angle. In CRYSTAL, radial and angular points
of the grid are generated through GaussLegendre and Lebedev
quadrature schemes. The grid size has a strong impact on both the
accuracy and cost of calculation, so that the tuning of the grid is
important to ensure numerical accuracy at an aordable cost. A
grid pruning is usually adopted, which is based on the observation
that the electron density at short radii has essentially spherical
symmetry and that, far from nuclei, the weights xr
Ai
; X
Aj
are
relatively small. Accordingly, the angular quadrature in pruned
grids is not radially uniform, that is, index j in the above expression
varies with i. In particular, the number of angular points is a
maximum in the valence region and decreases gradually away from
it in both directions. If properly designed, a pruned grid is expected
to be about as accurate as the corresponding unpruned grid and
much less expensive. In the following, the notation n
r
; n
X
will
indicate an unpruned grid with n
r
radial points and n
X
angular
points; the notation n
r
; n
X
p is used to indicate a pruned grid
having n
X
points on the Lebedev surface in the most accurate
integration region. The eect of the grid size on the calculation of
the vibrational frequencies has been extensively tested by using the
(55, 434)p, (75, 434)p, (75, 974)p, (75, 974) and (99, 1454) grids.
Results are shown in Table 1. As indicated by the maximum
(D
max
), minimum (D
min
) and average of the absolute (jDj) dier-
ences of the frequencies obtained with each grid with respect to
those of the most accurate (99, 1454) one (to be considered as fully
converged with respect to the grid size), the (75, 974)p grid per-
forms quite well at a reasonable cost, the latter depending upon the
number of points (N
p
) at which the function of the electron density
is evaluated. The accuracy of the calculation with dierent grids
can be estimated from the dierence (D
e
) between the number of
electrons in the cell (100, in the present case) and the value of the
integral of the electron density over the cell; as shown in Table 1,
the (75, 974)p, (75, 974) and (99, 1454) grids are essentially equiv-
alent. The eect of the grid size on the equilibrium geometry is
negligible: the calculated CO and CaO distances change at most
by 0.0003 A

when going from (55, 434)p to (99, 1454) and do not

change from (75, 974)p on.
The thresholds (ITOL1, ITOL2, ITOL3, ITOL4 and ITOL5)
controlling the accuracy of the calculation of Coulomb and
exchange integrals (Saunders et al. 2003) were set to 10
6
(ITOL1
to ITOL4) and 10
12
(ITOL5).
The diagonalization of the Fock matrix was performed at 32
points in the reciprocal space (Monkhorst net; Monkhorst and
Pack 1976) by setting the shrinking factor IS (Saunders et al. 2003)
to 6.
Central zone phonon frequencies
The BornOppenheimer potential energy surface V x of a system
is a function of the position xs of the N nuclei. For a nite system,
at the equilibrium nuclear conguration and within the harmonic
approximation, V x takes the form
1
The Crystal Web page: http://www.crystal.unito.it
560
V x
1
2
X
ij
u
i
H
ij
u
j
;
where the i; j summations run over all the 3N coordinates; u
i
rep-
resents a displacement of the i-th Cartesian coordinate from its
equilibrium value; H
ij
is the i; j element of the matrix of the
second derivatives of the potential, evaluated at equilibrium, with
respect to the displacement coordinates:
H
ij

1
2
@
2
V x
@u
i
@u
j

0
:
Phonon frequencies are then evaluated as the eigenvalues of the
weighted Hessian matrix W , whose i; j element is dened as
W
ij
H
ij
=

M
i
M
j
p
, where M
i
and M
j
are the masses of the atoms
associated with the i and j coordinates, respectively.
In periodic systems, the W matrix can be given a block-diagonal
form, each block being associated with a dierent q point in the
rst Brillouin zone [Wq]. The q 0 point (C point) is of special
importance, because IR and RAMAN spectra refer to this point.
Central zone (q 0) phonon frequencies are the eigenvalues of the
W0 matrix:
W
ij
0
X
G
H
0G
ij

M
i
M
j
p :
where H
0G
ij
is the second derivative of V x, at equilibrium, with
respect to atom i in cell 0 (translation invariance is exploited) and
atom j in cell G. By the way, once the Hessian matrix H is calcu-
lated, frequency shifts due to isotopic substitutions can readily be
calculated, at no cost, by accordingly changing the masses M
i
, in
the above formula. In the present case, the isotopic eects have
been estimated in the cases of substitution of
42
Ca for
40
Ca,
13
C for
12
C and
18
O for
16
O.
In CRYSTAL, energy rst derivatives with respect to the
atomic positions, v
j
@V =@u
j
, are calculated analytically (Doll
et al. 2001) for all u
j
coordinates, whereas second derivatives at
u 0 are calculated numerically using a two-point formula
(N 2):
v
j
u
i

0

v
j
0; . . . ; u
i
; . . .
u
i
;
or a three-point formula (N 3) to partially compensate for
anharmonicity:
v
j
u
i

0

v
j
0; . . . ; u
i
; . . . v
j
0; . . . ; u
i
; . . .
2u
i
:
In the present case, the inuence of either the number of points
used in the evaluation of the second derivatives (N 2; 3), or the
magnitude of the displacement u
i
of each atomic coordinate
(u 0:001; 0:002 A

) on the calculated frequencies has been

checked. Taking as a reference the N 2 and u 0:001 case,
jDj 0:6, D
max
1:7, D
min
1:7 cm
1
when N 3 is used; as
regards the step jDj 0:6; D
max
1:0; D
min
1:6 cm
1
when
u 0:002 A

.
Since the energy variations for the displacements here consid-
ered can be as small as 10
6
10
8
Hartree, the tolerance on the
convergence of the SCF cycles has been set to 10
10
Hartree.
In the case of ionic compounds, a correction must be added to
the Hessian in order to obtain the TOLO splitting. Such a cor-
rection takes into account long-range Coulomb eects due to
coherent displacement of the crystal nuclei (see Born and Huang
1954, Sects. 5, 10, 34, 35; see also Umari et al. 2001) and depends
essentially on the electronic (clamped nuclei) dielectric tensor
1
and on the Born eective charge tensor associated with each atom.
In the present case, the latter is evaluated through well-localized
Wannier functions (Baranek et al. 2001; Zicovich-Wilson et al.
2001, 2002; Noel et al. 2002) , whereas the former is from experi-
mental data (
xx
2:716,
zz
2:208; Deer et al. 1992).
Geometry
The lattice constants have been determined by minimizing the total
energy over the V ; c=a surface; for each V ; c=a pair, the internal
geometry (x fractional co-ordinate of O) was optimized by ana-
lytical gradient methods, as implemented in CRYSTAL (Civalleri
et al. 2001). At this stage, the grid used was (55 434)p. Since in the
calculation of the vibrational frequencies the localization of the
true energy minimum with respect to fractional coordinates is of
paramount importance, the internal geometry was reoptimized
with each dierent grid, by keeping the lattice constants at the
values rened at the rst stage. Geometry optimization is consid-
ered converged when the gradient (TOLDEG parameter in
CRYSTAL) is smaller than 0.00001 hartree bohr
1
and the dis-
placement (TOLDEX) with respect to the previous step is smaller
than 0.00004 bohr.
Results and discussion
The optimized geometry is reported in Table 2. The x
fractional coordinate of oxygen and the CO and CaO
distances displayed were calculated with the (75, 974)p
grid. The error with respect to the experimental datum is
small (about 1%) for the a parameter, dominated by the
covalent CO interaction; it is larger (1.6%) for the c
lattice parameter, determined by the interaction between
the two ionic subunits Ca
2
and CO
2
3
. The errors in the
calculated lattice parameters mirror the corresponding
ones for the C-O and CaO distances, that are about 1%
(CO) and 1.4% (CaO) larger than the experimental
distances.
Frequency of the normal modes
The rhombohedral cell of calcite contains two CaCO
3
formula units, for a total of N 10 atoms; the number
of vibrational normal modes (3N 3) is therefore 27.
The frequencies of such modes are listed in Table 3,
classied according to the symmetry they have in the 3m
point group (see below). The A
1g
and E
g
modes are
Table 1 Eect of the integration grid on the vibrational fre-
quencies. jDj, D
max
and D
min
are the average of the absolute dif-
ference, the maximum and minimum dierence with respect to the
reference case, the (99, 1454) unpruned grid, that can be considered
as fully converged. Np is the number of points in the grid and D
e
(in
l-electron) is the error in the integration of the charge density with
respect to the number of electrons per cell (100 in the present case).
DE is the energy dierence with respect to the reference case, in l-
hartree; d
CO
and d
CaO
are distances, in A

, as resulting from the

optimization of the x fractional coordinate of O with the various
grids
(55, 434)p (75, 434)p (75, 974)p (75, 974) (99, 1454)
jDj 13.3 5.9 0.3 0.3
D
max
47.5 19.1 0.4 0.2
D
min
)4.1 )1.3 )0.9 )0.9
Np 60 954 120 198 246 264 515 912 1 010 024
D
e
990 300 20 20 40
DE )1436 )104 )24 )26
d
CO
1.2948 1.2950 1.2947 1.2947 1.2947
d
CaO
2.3928 2.3927 2.3929 2.3929 2.3929
561
Raman-active, the A
2u
and E
u
are IR active, whereas the
A
1u
and A
2g
are spectroscopically inactive (silent modes).
The calculated frequencies are in general very close to
the experimental ones, the maximum error being
38 cm
1
and the absolute mean error being only
11:6 cm
1
. Errors are larger at the two extremes of the
vibrational spectrum, respectively in the range between
100 and 200 cm
1
and above 1400 cm
1
. In both cases
the calculated frequencies are higher than the experi-
mental ones. The overestimation might be due, among
other reasons, to the following two factors: limited
exibility of the basis set, that might inuence in par-
ticular the low-frequency modes, and the adopted
Hamiltonian (B3LYP), which is known to overestimate
by some percent the calculated frequencies in molecules
(Scott and Radom 1996), particularly at high frequency
values. It should be noted that, in the case of the very
low frequencies, temperature eects are known to have
some inuence; as the calculated spectrum refers to 0 K,
and the experimental one refers to room temperature,
the dierences might change if low-T experimental data
were available.
Catti and Pavese (1997) were able to calculate the
vibrational frequency of the A
1g
stretching CO mode, at
the HartreeFock level, by using a basis set similar to
the present one. The frequency value they obtained is
1210 cm
1
. The dierence (about 120 cm
1
) with respect
to both the present B3LYP calculation and the experi-
mental value, is likely to be due to the eect of the
Hamiltonian (HartreeFock is known to overestimate
frequencies by about 10%).
Lattice dynamical methods, based on parametric
model potentials, perform less well than the present ab
initio method: jDj 17:0, D
max
43 and
D
min
109 cm
1
(Pilati et al. 1998), and jDj 19:2,
D
max
31 and D
min
110 cm
1
(Pavese et al. 1992).
In both cases the largest error is for the longitudinal E
u
mode at 1549 cm
1
.
Analysis of the normal modes
According to Bhagavantam and Venkatarayudu (1969),
in calcite, where four almost independent groups can be
identied (two Ca
2
ions and two CO
2
3
units), vibra-
tional modes can be grouped into three categories,
namely: translatory type (T) and rotatory type (R)
external oscillations and internal (I) vibrations. External
vibrations involve relative translations of the four units
and librations of the carbonate ions, as a result of the
freezing within the crystal of real translations and
rotations of each single free unit. Internal vibrations are
those modes which involve deformation of the carbonate
groups. A symmetry analysis in the 3m point group
(Bhagavantam and Venkatarayudu 1969) shows that the
27 normal modes, classied as A
1g
2A
1u
3A
2g

3A
2u
4E
g
5E
u
, group themselves into 9 T modes of
symmetry A
2g
A
1u
A
2u
E
g
2E
u
, 6 R modes
of symmetry A
2g
A
2u
E
g
E
u
and 12 I modes of
symmetry A
1g
A
2g
A
1u
A
2u
2E
g
2E
u
. Due to the
very dierent strength of the intra CO
2
3
and interionic
forces, it might be expected that T and R modes have
lower frequencies than those associated with I modes.
Inspection of the eigenvectors of the Hessian matrix
and their graphical representations with the aid of the
Table 2 Calculated and experimental (Maslen et al. 1993
a
; Markgraf and Reeder 1985
b
) equilibrium geometry of calcite. The B3LYP
Hamiltonian and the (75, 974)p grid have been used
a (A

) c (A

) V (A

3
) c/a x d
CO
(A

) d
CaO
(A

)
Calc 5.0492 17.3430 382.9 3.435 0.25642 1.2947 2.3929
Exp
a
4.991(2) 17.062(2) 368.1(3) 3.419(2) 0.2573(2) 1.284(1) 2.3590(8)
Exp
b
4.988(1) 17.061(1) 367.6(1) 3.420(1) 0.2567(2) 1.280(1) 2.3595(5)
Table 3 Calculated (m
cal
) and experimental (m
exp
; Hellwege et al.
1970) Raman and infrared active vibrational frequencies (cm
1
). D
is the dierence m
cal
m
exp
. jDj, D
max
and D
min
are the average of the
absolute D, and the maximum and minimum D, respectively. Silent
modes are spectroscopically inactive. The B3LYP Hamiltonian and
the (75 974)p grid have been used
Mode Symmetry m
cal
m
exp
D
Raman
1 E
g
159.5 156 3.5
2 E
g
281.4 284 )2.6
3 E
g
707.2 712 )4.8
4 A
1g
1087.2 1086 1.2
5 E
g
1458.4 1434 24.4
Infrared
6 E
u
(TO) 129.3 102 27.3
E
u
(LO) 145.6 123 22.6
7 A
2u
(TO) 130.1 92 38.1
A
2u
(LO) 159.1 136 23.1
8 E
u
(TO) 221.5 223 )1.5
E
u
(LO) 230.6 239 )8.4
9 E
u
(TO) 286.7 297 )10.3
E
u
(LO) 376.4 381 )4.6
10 A
2u
(TO) 293.7 303 )9.3
A
2u
(LO) 395.8 387 8.8
11 E
u
(TO) 707.7 712 )4.3
E
u
(LO) 708.4 715 )6.6
12 A
2u
(TO) 867.6 872 )4.4
A
2u
(LO) 890.6 890 0.6
13 E
u
(TO) 1426.5 1407 19.5
E
u
(LO) 1566.1 1549 17.1
Silent
14 A
2g
197.6
15 A
1u
287.3
16 A
2g
310.4
17 A
2g
885.0
18 A
1u
1087.4
jDj 11.6
D
max
38.1
D
min
)10.3
562
graphical MOLDRAW program (Ugliengo et al. 1993)
shows that such a separation between external and
internal modes can indeed be made. Vibrations with
frequency in the range 700900 cm
1
mainly corre-
spond to bending I modes of the carbonate ions: the
two E
g
and E
u
modes (707.2 and 707.7 cm
1
, respec-
tively) are in-plane deformation of the planar CO
3
units, whereas the A
2g
and A
2u
modes (867.6 and 885.0
cm
1
) are out-of-plane deformations. The remaining
higher frequencies above 1000 cm
1
correspond to the
symmetrical (A
1g
and A
1u
) and asymmetrical (E
g
and
E
u
) stretching I modes of the carbonate. The vibra-
tional frequencies of the isolated CO
2
3
have also been
calculated at similar computational conditions. Such
frequencies are close to the corresponding ones in the
crystal, which is a conrmation of the above analysis;
in particular, the in-plane and out-of-plane deforma-
tions have frequencies of 658.1 and 877:9 cm
1
,
respectively; the symmetrical and asymmetrical stret-
ching modes have frequencies of 1004.1 and
1374:5 cm
1
. The frequency shifts due to isotopic
substitutions (isotopic eect), reported in Table 4, are
a further conrmation of the analysis of the I normal
modes: Ca is never involved in the modes discussed so
far, since no shift is observed when
42
Ca is substituted
for
40
Ca; A
1g
and A
1u
stretching modes involve only
oxygen motion, whereas all the other modes (bending
deformations) involve both carbon and oxygen atoms.
The small values of the dierence in the frequencies of
the g and u modes corresponding to the same defor-
mation within each CO
2
3
unit are to be noted; this is
a measure of the very weak coupling of the two car-
bonate ions to produce in-phase (E
u
, A
2u
and A
1g
) and
out-of-phase (E
g
, A
2g
and A
1u
) vibrations.
Concerning the external modes, apart from one case,
a clear-cut distinction between T and R modes cannot be
made: in general, vibrations with similar frequency and
same symmetry can couple to each other to give more
complex modes. The only pure T mode is the A
1u
at
287.3 cm
1
: indeed, since there are no A
1u
R modes, no
T R coupling exists and this vibration corresponds to a
pure translation-type mode.
The low-frequency A
1u
2A
2g
2A
2u
modes corre-
spond to relative translations of the carbonate and cal-
cium ions along [111] in the rhombohedral cell (z axis
henceforth) which are, except for the A
1u
mode, accom-
panied by librations of the carbonate planar unit around
the same axis. In particular, the A
2g
modes at 197.6 and
310.4 cm
1
are essentially out-of-phase translations of the
carbonate ions, with Ca ions at rest, whereas the two A
2u
modes at 130.1 and 293.7 cm
1
involve translations along
z of both calcium and carbonate ions. Within each
symmetry, the frequency dierence between the modes is
related to the dierent phase of the libration coupled with
the translation. The A
1u
mode at 287.3 cm
1
is the out-of-
phase translation of the two Ca ions along the z axis. This
analysis is corroborated by that based on the isotopic
eect, reported in Table 4: by substituting
42
Ca for
40
Ca,
no frequency shifts are observed in the A
2g
modes, thus
conrming that calcium is at rest. On the other hand, the
same substitution has some eect on the A
1u
and A
2u
modes, as it shouldbe expectedonthe groundof the above
analysis. The substitution of
18
Ofor
16
Ohas no eect only
in the case of A
1u
mode that, indeed, is the only one which
does not involve librations of the carbonate ions.
Of the two low-frequency E
g
modes, those at
159:5 cm
1
correspond to out-of-phase translations of
the carbonate ions parallel to the (111) plane of the
rhombohedral cell (xy plane henceforth); translations are
accompanied by in-phase librations of the two carbon-
ates units around one of the twofold symmetry axis
normal to z. The other E
g
modes at 281.4 cm
1
appear to
be in-phase librations of the carbonate ions around the
twofold symmetry axes. The E
u
modes at 129.3 and
221.5 cm
1
are translations of the Ca ions in the xy plane
accompanied by out-of-phase librations of the carbonate
units around the twofold symmetry axes. Finally, the E
u
modes at 286:7 cm
1
are relative translations of both Ca
and CO
3
units with out-of-phase librations of the latter
around the twofold symmetry axes. This analysis is in
agreement with the calculated isotopic eect (Table 4),
the latter showing that calcium ions are not involved in
E
g
modes, whereas they are in the E
u
ones. Moreover,
the
13
C-isotopic eect is stronger in all of the modes
involving CO
3
units translation, whereas it is weaker or
absent in the case of librations of the same units.
Conclusion
The feasibility of calculations of reliable vibrational
frequencies of crystal, at an ab initio level, has been
shown. At least in the case of calcite, the average error
Table 4 Frequency shifts (Dm, in cm
1
) due to isotopic substitu-
tions of
42
Ca for
40
Ca,
13
C for
12
C and
18
O for
16
O. The reference
frequencies m
ref
(in cm
1
) are those calculated for the most abun-
dant isotopes
40
Ca,
12
C and
16
O
Mode Symmetry m
ref
Dm
42
Ca
13
C
18
O
4 A
1g
1087.2 0.0 0.0 62.4
15 A
1u
287.3 7.0 0.1 0.0
18 1087.4 0.0 0.0 62.2
14 A
2g
197.6 0.0 0.7 10.5
16 310.4 0.0 2.3 14.9
17 885.0 0.0 25.8 12.5
7 A
2u
130.1 0.7 0.1 5.8
10 293.7 2.8 0.8 9.1
12 867.6 0.0 26.8 10.1
1 E
g
159.5 0.0 1.0 7.9
2 281.4 0.0 0.3 15.7
3 707.2 0.0 2.2 37.9
5 1458.4 0.1 42.1 20.8
6 E
u
129.3 0.8 0.0 5.5
8 221.5 4.9 0.0 1.1
9 286.7 3.0 0.6 9.4
11 707.7 0.1 2.4 37.7
13 1426.5 0.0 41.1 20.5
563
on the calculated frequencies, with respect to the
experimental data, is of the order of 10 cm
1
, which is
even slightly smaller than the average error obtained
with parametric model potential calculations. As a side
product of the calculation of the frequencies, the
eigenvectors of the Hessian matrix are obtained, whose
analysis proved to be a valuable tool in the interpreta-
tion of Raman and IR absorption spectra. The isotopic
eect can also be easily simulated; its analysis is an aid in
the interpretation of vibrational modes.
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