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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
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
.
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
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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