Phys. Chem.

Minerals 6, 305-312 (1980) PIIYSICS CHEMISIRY

MINERALS
© by Springer-Verlag 1980

Ab initio Calculation of Interatomic Force Constants

in H6Si207 and the Bulk Modulus
of g Quartz and g Cristobalite

M.D. Newton 1, M. O'Keeffe 2, and G.V. Gibbs 3

1 Department of Chemistry, Brookhaven National Laboratories, Upton, New York 11973, U.S.A.
2 Department of Chemistry,Arizona State University,Tempe, Arizona 85281, U.S.A.
3 Department of GeologicaI Sciences,Virginia PolytechnicInstitute and State University,
Blacksburg, Virginia 24061, U.S.A.

Abstract. Ab initio force constants calculated for S i - O stretch and Si...Si

non-bonded interactions in H6Si20 v are found comparable with experimen-
tal values derived from the lattice dynamics of ct quartz. The bulk moduli of
:~ quartz and c~ cristobalite are calculated using the molecular Si...Si force
constant and assuming rigid regular SiO 4 tetrahedra. In the case (c~ quartz)
where data are available the calculation agrees well with experiment.

Introduction

It has been recognized for some years now that bonding in crystals such as the
polymorphs of silica is not very different from that in small molecules involving
the same atoms. Thus S i - O bond lengths and SiOSi bond angles in crystalline
forms of SiO 2 are very close to those observed in molecules such as (H3Si)20. It
is not surprising therefore that a variety of molecular orbital calculations on
molecular fragments have shed considerable light on bonding and geometry in
crystals (cf. Tossell and Gibbs 1977, 1978; Meagheretal. 1979; Newton and
Gibbs 1980; Burdett 1980).
Developments in efficient computational algorithms for high speed com-
puters have made possible ab initio calculations on molecules containing
moderately heavy atoms such as Si. Recently a series of such calculations has
been used to determine the geometric and electronic structures of pyrosilicic
acid (Newton and Gibbs 1979, 1980). Optimization of the S i - O bond lengths in
the molecule for several SiOSi angles reproduces the linear d ( S i - O ) v s percent
s-character (in the oxygen bonding hybrid orbital) correlation observed for the
silica polymorphs (Newton and Gibbs 1980). In addition, the one-electron
energies calculated for pyrosilicic acid compare well with the vertical ion-
izational potentials measured for quartz (Newton and Gibbs 1979). The close
correspondence between observed bond lengths, angles and spectra of the silica
polymorphs with those calculated for pyrosilicic acid supports the view that
local bonding forces in the silica polymorphs are quite similar to those in the
molecule.

0342-1791/80/0006/0305/$01.60
306 M. O'Keeffe

Fig. 1. The H6Si207 molecule,showing the

distances L, q, and r. As described in the text,
both bridging and non-bridging Si- O bond
lengths were constrained to have a common
value, r

Whereas much of the emphasis in earlier MO studies on silicates has

involved geometrical parameters, it is also possible to study the energetics of
bonding in terms of force constants obtained from the same calculations.
Previous minimal basis S T O - 3 G calculations for first row atoms yielded useful
estimates of stretching and bending force constants for a variety of different
bonding situations (Newton et al. 1970).
Here we report on interatomic force constants obtained for pyrosilicic acid
and applied to the calculation of the bulk modulus of ~ quartz. The close
agreement between observed and calculated values presented below suggests
that bending of the SiOSi angle (changing the Si...Si distance) in the pyrosilicic
acid molecule provides a useful model for understanding the response of quartz
under confining pressure.

Force Constants

The structure of c< quartz consists of a continuous framework of symmetry

equivalent corner sharing silicate tetrahedra. Each tetrahedron is nearly regular
with two nonequivalent S i - O bonds (1.605 and 1.614 ~) and four nonequivalent
OSiO angles ranging from 109 to 111 ° (Levien et al. 1980). In addition, the SiOSi
angles between adjacent tetrahedra are all equivalent and measure 144°. In the
calculations reported here for H6Si20 7 (Fig. l), all the S i - O lengths were
constrained to be equal and the OSiO bond angles were maintained at the
tetrahedral angle, c o s - 1 ( _ 1/3), to conform with the regularity of the tetrahedra
in quartz. In addition, the SiOH angles were all kept at c o s - 1 ( _ 1/3), with the
O -- H bonds fixed at 0.96 •. The calculated energies (E) for three different Si - O
bond lengths and various SiOSi angles are reported in Table 1. An interesting
feature of these results is that although the minimum energy SiOSi bond angle
(0) is strongly dependent on the S i - O bond length (r) chosen, the Si...Si
distance (L) at the minimum energy varies by less than 0.03/~ (Table 2). The
same effect was previously observed in CNDO/2 calculations on the molecule
(SiH3)20 (Tossell and Gibbs 1978). This observation lends further support to the
idea previously expressed (O'Keeffe and Hyde 1976, 1978) that Si...Si in-
teractions are important in determining SiOSi geometries and that in particular
there will be only a relatively narrow range of Si...Si distances in the silica
polymorphs (3.0 to 3.2 •) (Hill and Gibbs 1979).
From the data one can calculate a force constant for deformation of the
SiOSi angle. This may be expressed either as a Si... Si interatomic force constant
Calculation of the Bulk Modulus of Quartz 307

Table 1. The energy (E) of H6Si207 for

r(A) 0(deg) E(atomic units)" different S i - O bond lengths (r) and SiOSi
angles (0)
1.65 125 -1091.76575
1.65 130 - 1091.76632
1.65 135 -1091.76601
1.62 140 -1091.76261
1.62 135 -1091.76274
1.62 130 -1091.76221
1.59 140 -1091.74841
1.59 145 -1091.74858 " These energies are significant to the
1.59 150 -1091.74839 figures quoted (1 atomic unit=
2.625 x 103kJmole 1)

Table2. Derived force constants and minimum energy SiOSi angles

(0rain) and Si...Si distances (Lmln)for H6Si20 7 at different S i - O
bond lengths

r AL(Nm-l) A0(Nm 1) 0min(deg) Lmin(•)

1.65 102 17.9 130.5 2.997
1.62 94.8 13.1 136.3 3.007
1.59 89.1 8.21 144.6 3.029

AL = 02 e / ~ L 2 (~)

or as an angle b e n d i n g force c o n s t a n t 1

Ao = (~2 E/e 02)/r 2. (2)

The results are collected in T a b l e 2 . It is interesting to note t h a t A L is n e a r l y

c o n s t a n t over the r a n g e of r values considered, a result which is c o m p a t i b l e with
o u r belief t h a t SiOSi configurations are better discussed in terms of S i . . . S i
i n t e r a c t i o n s r a t h e r t h a n in terms of the SiOSi angle, 0. The n o n - b o n d e d
repulsions seem to be d o m i n a t e d b y Si... Si i n t e r a c t i o n s r a t h e r t h a n interactions
b e t w e e n the closest oxygen a t o m s of a d j a c e n t t e t r a h e d r a (Fig. 1). This assertion
is b o r n e out b y negative o v e r l a p p o p u l a t i o n s c a l c u l a t e d for the n o n - b o n d e d
a t o m s in H 6 S i 2 0 7 (Fig.2). T h o s e c a l c u l a t e d for the Si a t o m s in the SiOSi
l i n k a g e [ n ( S i . . . S i ) ] increase in m a g n i t u d e r a p i d l y with decreasing angle a n d
S i . . . S i s e p a r a t i o n . O n the o t h e r h a n d , those c a l c u l a t e d b e t w e e n the intertetra-
h e d r a l oxygens in closest c o n t a c t [n(0... 0)] are negligible until the c o r r e s p o n d i n g
0 . . . 0 s e p a r a t i o n s are < 3 . 3 •. F u r t h e r m o r e , the m a g n i t u d e s of n ( 0 . . . 0 ) are less
t h a n the c o r r e s p o n d i n g In(Si...Si)l values by at least an o r d e r of m a g n i t u d e for
the entire range of SiOSi angles d i s p l a y e d in Fig. 2. T h e calculations were b a s e d
on a S i - O distance of 1.62A, which is the m e a n value r e p o r t e d b y L i e b a u

i Several different definitions of angle-bending force constants are current. The one adopted here
has the merit of having the same dimensions (force/length) as inter-atomic force constants
308 M.O'Keeffe

~ "2.66
-oo,p

- 0.04 [ d(Si-O)=1.62/~[

Fig. 2. Non-bonded overlap populations n(Si... Si) and

~c:-0.06 /2.94 ,,1.U D

n(0... 0) calculated for H6Si207 as a function of SiOSi

angle, based on r= 1.62A (see Fig. 1); 0...0 refers to a
closest-contact inter-tetrahedral pair (there are two such
o2.81 pairs in the mm(C2v ) geometry adopted in the present
study (Fig. 1)). The numbers on the curves are the
- 0.08 corresponding Si... Si and 0... 0 distances
120 1/.0 160 180
LSiOSi

(1969) for silicate tetrahedra. A more general discussion of the significance of

overlap populations for silicates is given by Newton and Gibbs (1980).
In addition to providing A c and A o [Eqs.(1) and (2)], the present calcu-
lations can also be used to determine the variation of energy with r at constant
L. This is of interest because as noted above, the calculated (Table2) and
observed (O'Keeffe and Hyde 1978) equilibrium values of L are found to be
close to 3.0/~, irrespective of the value of r. For H6SizOv this means that
8 S i - O bonds are changed and at the same time 12 (intra-tetrahedral) nearest
neighbor 0 . . . 0 distances (q) are changed. As q = ( 8 / 3 ) 1/2 r it follows that

(82 E/SrZ)L, ~ = 8 A r + 32 Aq. (3)

Here the subscript ? refers to the constraint of regular silicate tetrahedra, and Ar
and Aq are the force constants for S i - O and 0 . . . 0 interactions evaluated at the
equilibrium geometry. With L maintained at 3.0/~ we find (using a finer grid of
data than reported in Table 1):

A~+4Aq=0.54 x 103 N m -1.

As mentioned above, a major motivation for this work is to test the

applicability of data calculated for small molecules to the calculation of proper-
ties of crystals. It is of interest therefore to compare the force constants
determined here with those derived from force-constant models of the lattice
dynamics of quartz. The most recent and complete of these models are those of
Striefler and Barsch (1975) and of Barronetal. (1976). Barronetal. (1976) used
two short range force models (E2 and E3) that differed mainly in that model E3
included non-nearest neighbor 0...0 interactions; these additional force con-
stants were less than 1 0 ~ of nearest neighbor terms and of dubious physical
Calculation of the Bulk Modulus of Quartz 309

Table3. Comparison of force constants calculated from H6Si20 7 with those derived from the lattice
dynamics of quartz (all in N m -~)

Force constant H6SizOv a E2 b E3 b SB c I a

A~ 381.7 399.8 479.0 467.0

Aq 48.8 50.6 24.7 64.1
Ar + 4Aq 540 577 602 578 723
AL 92.6 e i20.5 78.8 - 48.2

This work
b Barron et al. (1976)
c Striefler and Barsch (1975)
d Iishi (1978)
° Interpolated for r = 1.61 • from the data of Table 2

significance, as suggested by the authors. Streifler and Barsch used a force

constant for SiOSi bending that included a component of bond stretching and
thus is not readily comparable to our constants. More recently Iishi (1978)
treated just the zone center frequencies of quartz with a polarizable-ion model
that also included short range force constants. Table3 collects the force con-
stants derived in different ways for comparison. Although force constants
derived from lattice dynamics are notoriously model dependent, they are in
rough agreement with our calculated values. This agreement between theory and
experiment suggests that molecular orbital calculations can be fruitfully used to
determine the short range force field appropriate for crystals such as quartz.
Even at this stage we can hypothesize that in quartz the short-range non-bonded
force constants fall in the sequence S i . . . S i > 0 . . . 0 (intra-tetrahedral)~>0...0
(inter-tetrahedral), as inferred qualitatively from the magnitudes of the cor-
responding S T O - 3 G antibonding overlap populations (]n(Si...Si)l>ln(intra-
tetrahedral 0... 0)1 ~>[n(inter-tetrahedral 0... 0)1) calculated for pyrosilicic acid.

The Bulk Modulus of Quartz and Cristobalite

The bulk modulus of a crystal at zero temperature can be expressed as

K = v(8 2 E/Sv2), (4)

where v is the unit cell volume. In a short-range-force model the energy is

considered to depend only on such coordinates as bond lengths, non-bonded
distances and, possibly, bond angles. Thus for quartz or cristobalite we might
consider explicitly the variables r, q, L, and the OSiO bond angle. Symbolizing
these by X¢ we can write (4) as

2 ~y26~E2 [dXi~ ~i 8E d 2 X i (5)

2

where the cross second derivatives (82 E/SX iSXJ) are omitted because they are
in general much smaller than the 82 E/SX 2 terms. Furthermore, at zero pressure,
the second term must be zero for the equilibrium structure.
310 M. O'Keeffe

In the quartz and cristobalite structures, the framework of corner-connected

silicate tetrahedra can be collapsed (reduced in volume) by concerted rotations
of the tetrahedra about axes through their centers in such a way that all SiOSi
angles change by the same amount without distorting the tetrahedra. Thus it is
expected that the major effect of moderate pressure on these structures will be to
change 0 and hence L. In particular, terms such as (dr/dr) 2 and (dq/dv) 2 are
expected to be much smaller than ( d L / d v ) 2. In the case of quartz, recent high-
pressure studies (Jorgensen 1978; Levienetal. in press) have shown that indeed
this assumption is correct, but we do not use the results of these studies
explicitly here.
Equation(5) becomes then for the quartz and cristobalite structures

K = z v(dL/dv) 2 A L (6)

where z is the number of Si... Si nearest-neighbor distances per unit cell (z = 6

for ct quartz and z = 8 for ~-cristobalite).
To obtain the factor ( d L / d v ) 2 in Eq. (6) we can approximate the structures by
ones with regular silicate tetrahedra. ~ Quartz has been described from this
point of view by Grimm and Dorner (1975) and by Fischer and Zemann (1975),
and ~ cristobalite similarly by Fischer and Zemann (1975) and by O'Keeffe and
Hyde (1976).
In c~ quartz all the structural parameters can now be related to the angle ~b
by which the tetrahedra are rotated about (100) from their positions in /~
quartz. In terms of the SiOSi angle, 0,

~b= cos-1 [ ( 3 / 4 - cos 0) 1/2 - 1/]fi2] (7)

and

z v(dL/dv) 2 = 3 cos q~(1 + 2 lf3 cos q~)2 _- f(q~) (8)

4 r(1 + 3 lf3 cos ~b)2(1 + i f 3 cos ~b+ 3 cos2 qS) r

Similarly for ~ cristobalite, if q5 is now the angle by which tetrahedra are

rotated about (100) from their positions in the idealized high cristobalite (C9)
structure, then

~b= cos - 1 [ ( 3 / 4 - (3 cos 0)/2) I/2 - 1/2] (9)

and

zv(dL/dv)2 = If3 cos q5(1+ 2 cos q~)2 _g(~b) (10)

8 r(1 + 3 cos q5)2(1+ cos qb+ cos2 qb) - r

Equations (7)-(10) are either given by or derived from equations given by Grimm
and Dorner (1975) and O'Keeffe and Hyde (1976).
As can be seen from Table 4, the functions f(~b) and g(~b) depend only weakly
on ~b (or 0); thus in evaluating K from Eq. (6), one need really only assume a
value for the S i - O bond length r. Thus the bulk modulus of ct quartz and
Calculation of the Bulk Modulus of Quartz 311

Table4. The functions f(~b)

and g(~b)for ~ quartz and c~quartz ~ cristobalite
c~cristobalite
0 ~ f(4) 4 g(4)

150° i0.7 ° 0.0685 21.3° 0.0410

145° 15.4° 0.0691 24.9° 0.0411
140° 19.5o 0.0698 28.6° 0.0413

c r i s t o b a l i t e can be c o n s i d e r e d as c a l c u l a t e d entirely from d a t a derived from ab

initio calculations on small molecules, a s s u m i n g a value of r a p p r o p r i a t e to the
p a r t i c u l a r species of interest. W i t h r = l . 6 1 x 1 0 - 1 ° m a n d A L = 9 2 . 6 N m 1 (see
f o o t n o t e e of T a b l e 3), we o b t a i n finally

for c~ q u a r t z K = 3 . 9 7 x 10 t° P a
for ~ cristobalite K = 2.36 × 101 o Pa.

T h e b u l k m o d u l u s of c~ quartz, b a s e d on an e x t r a p o l a t i o n to T = 0 by S o g a
(1968) of the d a t a of M c S k i m i n e t a l . (1965) is 3.93x 1 0 1 ° p a . O u r c a l c u l a t e d
value is no d o u b t fortuitously close (indeed the force c o n s t a n t A r is given with
e x a g g e r a t e d precision); nevertheless the a g r e e m e n t is very gratifying. W e k n o w
of no m e a s u r e m e n t of K for ~ cristobalite; our p r e d i c t i o n is sufficiently different
from t h a t of ~ q u a r t z to m a k e such a m e a s u r e m e n t worthwhile.

Summary

The p r i n c i p a l a s s u m p t i o n s m a d e in this p a p e r are:

1. Useful estimates of i n t e r a t o m i c force constants in molecules such as
H 6 S i 2 0 7 are o b t a i n e d from ab initio calculations at the S T O 3 G level.
2. These force c o n s t a n t s are transferable to crystals (such as quartz) with the
s a m e b o n d lengths a n d angles.
3. In ~ q u a r t z a n d c~ cristobalite, the d o m i n a n t c o n t r i b u t i o n to the b u l k
m o d u l u s is m a d e by the force c o n s t a n t a s s o c i a t e d with the b e n d i n g of the SiOSi
group. W e have expressed this force c o n s t a n t in terms of the Si... Si n o n b o n d e d
interaction.
W e have used these a s s u m p t i o n s , b u t no e x p e r i m e n t a l d a t a (other t h a n
f u n d a m e n t a l a t o m i c c o n s t a n t s a n d the a p p r o p r i a t e SiO distance), to calculate
the b u l k m o d u l u s of c~ quartz. T h e close a g r e e m e n t with e x p e r i m e n t that we find
leads us to believe t h a t the three a s s u m p t i o n s d e t a i l e d a b o v e are basically
sound.

Acknowledgments. This work was supported in part by the National Science Foundation, grants
DMR78 09197 and EAR77 23114 and was carried out in part while one of us (GVG) was a
Distinguished Visiting Professor in the Department of Chemistry at Arizona State University during
1979. The work was also supported in part by Brookhaven National Laboratory under contract with
the U.S. Department of Energy and supported by its Office of Basic Energy Sciences. We thank Dr.
Louise Levien for a thorough and helpful review of the paper.
312 M. O'Keeffe

References

Barron, T.H.K, Huang, C.C., Pasternak, A.: Interatomic forces and lattice dynamics of c~-quartz. J.
Phys. C: 9, 3925-3940 (1976)
Burdett, J.K.: How some simple solids hold together: The use of the fragment formalism in crystal
chemistry. J. Am. Chem. Soc. 102, 450 (1980)
Fischer, R., Zemann, J.: Geometrische und electrostatische Berechnungen am Quarz- und am
Cristobalit-Type. I. Modelle mit AB 4 Tetraedern der Symmetric 743rn. Tschermaks Mineral.
Petrogr. Mitt. 22, 1-14 (1975)
Grimm, H., Dorner, B.: On the mechanism of the c~-/~phase transition in quartz. J. Phys. Chem.
Solids 36, 407-413 (1975)
Hill, R.J., Gibbs, G.V.: Variation in d(T-O), d(T...T) and /TOT in silica and silicate minerals,
phosphates and aluminates. Acta Crystallogr. Sect. B:35, 25-30 (1979)
Iishi, K.: Lattice dynamical study of the e-/~ quartz phase transition. Am. Mineral. 63, 1190-1197
(1978)
Jorgensen, J.D.: Compression mechanisms in c~-quartz structures SiO 2 and GeO 2. J. Appl. Phys. 49,
5473-5478 (1978)
Levien, L., Prewitt, C.T., Weidner, D.J.: Single-crystaI X-ray study of quartz at pressure. Am.
Mineral. 65, (1980)
Liebau, F.: Silicon. In: Handbook of geochemistry, Vol. II, Wedepohl, K.H. (ed.). 1969, 14-A-2
McSkimin, H.J., Andeatch, P., Thurston, R.N.: Elastic moduli of quartz versus hydrostatic pressure
at 25° and -198.5°C. J. Appl. Phys. 36, 1624-1632 (1965)
Meagher, E.P., Tossell, J.A., Gibbs, G.V.: A CNDO/2 molecular orbital study of the silica
polymorphs (abstr.). Abstr. Progr. 9, 1092 (1972)
Newton, M.D., Gibbs, G.V.: A calculation of bond length and angles, force constants, vertical
ionization potentials and charge density distributions for the silicate ion in H4SiO4, H6Si20 7
and H6Si20 (abstr.). EOS 60, 415 (1979)
Newton, M.D., Gibbs, G.V.: Ab initio calculated geometries and charge distributions for H4SiO 4
and H6Si20 7 compared with experimental values for silicates and siloxanes. Phys. Chem.
Minerals 6, 221-246 (1980)
Newton, M.D., Lathan, W.A., Hehre, WJ., Pople, J.A.: Self-consistent molecular orbital methods. V.
Ab Initio calculation of Equilibrium Geometries and Quadratic Force Constants. J. Chem. Phys.
52 (No. 8), 4064-4072 (1970)
O'Keeffe, M., Hyde, B.G.: Cristobalites and topologically-related structures. Acta Crystallogr. Sect.
B :32, 2923-2936 (1976)
O'Keeffe, M., Hyde, B.G.: On S i - O - Si configurations in silicates. Acta Crystallogr. Sect. B :34, 27-
32 (1978)
Soga, N.: Temperature and pressure derivatives of isotropic sound velocities of e-quartz. J. Geophys.
Res. 73, 827-829 (1968)
Striefler, M.E., Barsch, G.R.: Lattice dynamics of c~-quartz. Phys. Rev. Sect. B :12, 4553-4566 (1975)
Tossell, J.A., Gibbs, G.V.: Molecular orbital studies of geometries and spectra of minerals and
inorganic compounds. Phys. Chem. Minerals 2, 21-57 (1977)
Tossell, J.A., Gibbs, G.V.: The use of molecular-orbital calculations on model systems for the
prediction of bridging-bond-angle variations in siloxanes, silicates, silicon nitrides and silicon
sulfides. Acta Crystallogr. Sect. A :34, 463-472 (1978)

Received April 3, 1980