J. Phys. D: Appl. Phys. 24 (1991) 89-99.

Printed in theUK
1 Application of Bravais-Friedel-,
I Donnay-Harker, attachment energy
I
and ki ng models to predicting and
I understanding the morphology 04
1 molecular crystals
R Dochertyt, G Clydesdale*, K J Roberts$ and P Bennemall
t IC1Colours and Fine Chemicals Research Centre, Hexagon House, Blackley,
Manchester M93DA, UK
* Department of Pure and Applied Chemistry, Strathclyde University,
Glasgow GI IXL, UK
11 RIM Laboratory of Solid State Chemistry, Faculty of Science,
University of Nijmegen, Toernoovield, Nijmegen. The Netherlands
Received 20 J une 1990, in final form16 October 1990
Abstract. The development of structural models for predicting the external
morphology of crystalline materials ispresented and discussed in terms of their
applications to molecular crystals. The predicted crystal morphologies of a number
of molecular materials including a-sul phur, naphthalene, benzoic acid and
hexamine are presented using the Bravais-Friedel-Donnay-Harker, anachment
energy and king models. The results of the various models are compared both
against each other and against the experimentally Observed morphologies.
1. Introduction
The external morphology of crystals and its relation-
ship to internal crystal structure has long been of inter-
est to chemists. The increasing importance of
understanding the purification and crystallization of
speciality chemicals such as colours and pigments,
agrochemicals, pharmaceuticals etc has led to a de-
veloping interest in understanding both crystal mor-
phology and morphological stability of molecular
materials. Morphological factors can have significant
effects in both the production and post-production
properties of such materials. Factors such as the sep-
aration, handling, packaging and storage of crystalline
products can all depend significantly on crystal mor-
phology. This can have many economic ramifications,
for example:
(i) crystals which are difficult to filter cause reduced
separation efficiency;
(ii) crystal shape must allow free flow of particulate
solids under processing conditions as attrition and frag-
mentation are likely to result in the creation of haz-
ardous dusts;
5 Alsa SERC Daresbury Laboratory. Warrington WA4 4AD, UK.
0022-37271911020089 +11 $03.50 0 1991 IOP Publishing Ltd
(iii) for optimum packing and storage conditions
crystal shape must allow maximum packing density and
reduce any problems associated with caking;
(iv) for pharmaceutical materials in particular the
dissolution rate is important and this depends on sur-
face area which is dependent on crystal shape.
Molecular crystals are formed by relatively weak
van der Waals intermolecular forces with in some cases
considerably stronger hydrogen-bonds. For molecular
materials the weak van der Waals intermolecular inter-
actions do not substantially differ between fluid and
solid states and thus simulations of growth morphology
based on crystal structure are often quite good (Hart-
man 1973, Human er al 1981, J etten er a[ 1984, Doch-
erty and Roberts 1988).
I n this paper we overview the structural models
for morphological prediction together with examples
which illustrate the nature, complexity, assumptions
and limitations of each simulation. The models are
compared both against each other and against observed
morphologies. This work overviews recent devel-
opments in the authors laboratories which have been
directed towards the use of morphological simulation
as a routine tool for computational chemists and crystal
growers to understand, optimize and control the mor-
phology of molecular crystals.
89
R Docherty et a/
Nucl eat i on cent re
(1907) and Donnay and Harker (1937). These laws are
often quoted together as the BFDH law which can be
summarized thus: taking into account submultiples of
the interplanar spacing dhxl due to space-group
symmetry, the most important crystallographic forms
will have the greatest interplanar spacings. Using the
BFDH principle and given the unit cell dimensions,
space group and hence extinction conditions it is fairly
trivial to predict the morphological importance. From
the BFDH prediction the reciprocal of the slice thickness
is used as a measure of growth rate for the Wulff
plot simulation of the BFDH morphology. This method
makes use .of the framework of the crystal lattice and
no consideration is given to the atom or bond type or
to the partial charge, all of which must have an effect
during crystal growth.
in sur f ace ener gy
Figure 1. Schematic representation of the classical Wulfl
plot lor the derivation of equilibrium form.
2. Morphological modelllng based on crystal
structure
2.1. Equilibrium form-the Wulff plot
Early crystallographers were fascinated by the plane-
ness and symmetry of the external shape of many syn-
thetic and naturally crystallized solids which led them
to postulate that the shape was the result of an ordered
internal arrangement of the constituent atoms. Hauy
(1792) showed that polyhedral crystal shapes could be
built up by stacking cubes (unit cells) in a variety of
three-dimensional sequences. Gibbs (1875) proposed
that the polyhedral shape of a crystal will be such as
to minimize the total free energy, i.e.
I: Y ~ A , =minimum (1)
where y, and A, are the surface energies and areas
of the ith face respectively. Wulffs (1901) theorem
extended this idea and suggested that the equilibrium
form would be bounded by faces located at distances
from the growth origin proportional to the surface
energies of the faces. The resulting Wulff plot shown
in figure 1 is simply a three-dimensional polar plot of
surface energy as a function of the crystal orientation.
From Gibhs theorem it follows that a construction
of planes tangent to the cusp minimum will give the
equilibrium form and that this will be a polygon.
Wulff plots can be prepared using the gnomonic
projection (e.g. Philips 1963) and nowadays this pro-
cess is greatly aided by the availability of dedicated
computer programs.
2.2. Using lattice geometry and symmetry: the Bravais-
Friedel-Donnay-Harker ( B ~ H ) model
Morphological simulations based on crystal lattice
geometry were proposed by Bravais (1866), Friedel
90
2.3. Models using surface bonding
2.3.1. Calculating intermolecular interactions. To
assess the effect of energetics on morphology it is
necessary to evaluate the interaction energies between
the crystallizing entities. The interaction energy V,
between two non-bonded atoms i and j is given by
functions such as the Lennard-J ones 612 potential
(equation (2)) and the Buckingham h x p potential
(equation (3)):
V. . 4 =-A/r& t B/rf +qiqj/Drg (2)
V, . $1 =- A/ r$ +Bexp(-Cr,l) +qjqj/Dr,l (3)
where the first two terms in each equation describe
the repulsive and attractive van der Waals interactions
respectively and the third term describes any elec-
trostatic interactions; A, B and C are parameters
specific to particular atom-atom interactions; qi and q,
are the fractional charges on atoms i and j separated
by a distance rij and D is the dielectric constant. In
some cases additional hydrogen-bonding parameters
may have to be added to complete the description of
the interactions.
For thc work prcscntcd in this papcr various atom-
atom potentials were used (Williams 1966, Momany et
al 1974, Lifson er al 1979). Fractional charges were
calculated using the program MNDO (Dewar and Theil
1979) except when Lifson er ais potential was used, as
this includes charge values (Set 111 in this reference
was used). To describe hydrogen-bonds Momany et al
used a 1&12 potential similar to the Lennard-J ones (%
12 potential. Lifson et ai found no special hydrogen-
bond potential to be required. The selection and
sources of atom-atom potential functions for mor-
phological calculations in molecular systems have been
detailed elsewhere (Docherty and Roberts 1988).
Summing the intermolecular interactions between
a central molecule and each of the surrounding mol-
ecules within the crystal yields the lattice energy E,,.
Using the atom-atom approximation each intermol-
ecular interaction can be considered to be the sum of
the constituent atom-atom interactions (e.g. Busing
Structural models for morphological prediction
1983, Williams 1983). If there are n atoms in the central
molecule and n atoms in each of the N surrounding
molecules then:
N n n
E,, =i c c E Vkij. (4)
k = , i = , j = l
2.3.2. Periodic bond chains and attachment energy.
Hartman and Perdok (1955) were the first to exten-
sively quantify crystal morphology in terms of the inter-
action energy between crystallizing units. They used
the assumption by Born (1923) that surface energy
is directly related to the chemical bond energies and
identified uninterrupted chains of strong intermol-
ecular interactions called periodic bond chains (PBCs).
They defined the flat F faces observed on as-grown
crystals to contain at least two PBCS lying in the surface
plane.
PBC analyses can he used to determine slice (E,,,,,)
and attachment ( Ea, , ) energies. E,,icr is defined as the
energy released on the formation of a growth slice of
thickness dhk, (Hartman 1973, Hartman and Bennema
1980, Berkovitch-Yellin 1985). E,,, is defined as the
fraction of the total lattice energy released on the
attachment of this slice to a growing crystal surface,
i.e.
Ecr =Es~i ce +Eat,. ( 5 )
Faces with the lowest attachment energies will be the
slowest growing and therefore have the most mor-
phological importance (Hartman and Bennema 1980).
This is particularly true at low supersaturations when
the birth-and-spread and BCF (Burton, Cahrera and
Frank 1951) growth mechanisms dominate crystal
growth.
Attachment energy calculations can be carried out
by partitioning the lattice energy between the slice and
attachment energies (Berkovitch-Yellin 1985). Slice
and attachment energies can he calculated by summing
the interactions between a central molecule and all the
molecules within and without, respectively, a slice of
thickness dhk, as shown schematically in figure 2. The
selection of the suitable slices ( hkl ) for these cal-
culations can be deduced from a BFDH analysis.
This attachment energy (AE) model assumes that
the surface is a perfect termination of the hulk and that
no surface rearrangement takes place. This has been
shown to have a significant effect in the cases of inor-
ganic systems such as m-AI2O3 and a-Fe,O, (Mackrodt
et a/ 1987). Studies of organic systems by Berkovitch-
Yellin (1985) and Docherty and Roberts (1988) seem
to indicate that here the effect of surface relaxation is
probably negligible.
2.4. Surface roughening-the king (IS) model
The concept of surface roughening during crystal
growth was first introduced by Burton et a/ (1951) and
J ackson (1958) who predicted a transition between or-
dered layer growth on a smooth surface and rough
disordered growth. Monte Carlo models (e.g. Gilmer
and J ackson 1977) can be used to simulate the surface
roughening although the calculations are currently
restricted to fairly idealized systems and are thus not
suitahle for molecular crystals. However, van Beijeren
(1977) has shown that statistical mechanical king (IS)
models (e.g. van der Eerden et al 1978) can he used
to simulate surface roughness. In the layer interface
model the solid and fluid regions at the growth
interface are separated by a single layer consisting of
a mixture of solid and fluid blocks. This one-layer
model is a real two-dimensional bulk phase which
exhibits an order-disorder phase transition at a critical
temperature 8. Onsager (1944) showed that the critical
temperature for this two-dimensional king net can he
solved analytically.
In the application of Ising models to crystal mor-
phology the nodes of the two-dimensional connected
nets are the centres of gravity of the constituent mol-
ecules in the crystal structure, with the links between
the nodes being the intermolecular bond strengths. The
critical king temperature for such simple nets is given
by:
o c =2/03 ( 6)
where 13 is the critical value of the average dimen-
sionless bond energy 03 given by
(7)
where m is the number of bonds originating from a
node and cpf is the bond strength of the ith connection.
For a rectangular net, given a series of relative bond
strengths, it is possible to calculate 8. Onsagers theory
was extended and generalized to very complicated
planar connected nets by Rijpkema et al (1983) and 8
for a real crystal system can be determined by:
(i) identifying the strong bonds in the crystal struc-
ture and calculating their relative bond strengths;
(ii) derivation of the connected nets of the impor-
tant crystallographic forms;
(iii) conversion of the connected nets into rect-
angular nets;
(iv) the use of the bond energies and rectangular
nets to calculate 0;
(v) the use of the reciprocal of these values to com-
pute the theoretical morphology.
The IS model reflects the stable crystal morphology
close to the growth conditions for kinetic roughening
(i.e. at the transition from a smooth to a rough
interface). Thus it should be considered to be a stab-
ility model. By reflecting the morphology of the crystal
just below the critical roughening temperature it pro-
vides an important benchmark for assessing the inter-
relationship between morphology and supersaturation.
For materials crystallized at low supersaturations, faces
additional to and less thermodynamically stable than
those predicted by the IS model will he able to grow
without significant surface roughening.
91
R Docherty et a/
Li mi t i ng r odi ur
t o r r unmot i on
A i s t he c en t r al m o I e c ~ I e
0i r o mol ecul e i n t he c r y r t d out of t he s l i c e
D is o molecule i n t he d i c e
N i r t h e g r a v t h normal t o t h e p l n n e r l h k l l
A0 and AD ~ r e ' b o n d i n g v ec t or s '
dhkl i s t h e i nt er pl mmr spor i ng
B i i :he ; ngk k t v e e f i :h g;z-:b iloiinai ail6 iilr bonhng v r i i o r
AC i s t he component o f :he vect or AB por ol l el t o N t h e gr owt h nom01
Figure 2. Schematic diagram showing the partition of slice
and attachment energies.
3. Examples of some morphological predictions
In this section examples of some morphological pre-
dictions of molecular crystals carried out using the
models described above are presented. The example
of naphthalene is used with all models and the various
predicted morphologies thus produced are compared
in section 4. Calculations using the BFDH, AE and IS
models were carried out using the computer programs
MORANG (Docherty er a1 1988), HABIT (Clydesdale er a1
1990) and TCCALC (Rijpkema 1984) respectively. HABI T
was also used to calculate lattice energies for the assess-
ment of the validity of the chosen intermolecular
potentials. Morphological drawings were prepared with
the aid of the program SHAPE (Dowty 1980). Further
details are also given in appendices A.l -AS and else-
where (Docherty er a1 1990). The basic approach used
to model the morphologies is illustrated by the flow-
chart in figure 3.
3.1. The BravaisFriedel-Donnay-Harker model
3.1.1. a-Sulphur. a-Sulphur crystallizes in the ortho-
rhombic space group Fddd with sixteen sg rings in a
unit cell of dimensions a =10.4646, b =12.866 and c =
24.486 8, (Caron and Donahue 1965). The morphology
of sulphur is dominated by the 1111) and (001) forms
92
Colrulrrte l ot t i r e energy ond
c ompor e agoi ns: subl i mat i on
ent hal py- r et i ne dei ci i pt i en
Ident i f y st rong bond$
i n cryst al st r uct ur e
Exami ne 30 pocking
Calculate sl i ce and at t achment det ermi ne connect ed
nets and obt ai n 0c energi es f or t he most i mport not
BFDH forms I HA B I TI
t
Conpor e u i t h observed morphol ogi es
Figure 3. Schematic showing the basic approach for
carrying out morphological calculations. Path A produces
model.
the BFDH model, path B the AE model and path C the IS
with {113), {all), (100) and {101} forms occasionally
observed (Groth 1906, Hampton er a1 1974). These
morphologies are shown in figures 4( a) and (b).
The space group Fddd includes extinction con-
ditions expressing both the face-centred mode of the
lattice and the presence of d-glide planes (International
Tables for X-ray Crystallography 1983). The import-
ance of allowing for translational symmetry elements
through the BFDH model is clearly illustrated in the
simulated morphologies predicted assuming no con-
ditions (figure 4(c)), face centring only (figure 4(4)
and both face centring and glide planes (figure 4(e)).
The change in morphological importance associated
with the various symmetry elements is shown in table
1. The data show, for example, that the dominant {I l l )
growth form is the ninth most important when no con-
ditions are applied. Thus the resultant Wulff plot
shown in figure 4(c) bears little relation to the observed
morphology. After applying the face-centring con-
ditions (figure 4(d)) (111) becomes the second most
important form and the resultant Wulff plot predicts
the important forms but with an incorrect aspect ratio.
Adding the condition for the d-glide planes predicts
the 1111) form to become the most important and pro-
vides an excellent correlation between the predicted
morphology (figure 4(e)) and the observed mor-
phologies (figure 4(a) and (b)).
3.1.2. Naphthalene. Naphthalene (CloHlo) is an aro-
matic hydrocarbon which crystallizes in the monoclinic
Structural models for morphological prediction
iOOli
3.2. Attachment energy model
3.2.1. Assessment of intermolecular potentials. Figure
6 shows the calculated values for the lattice energy of
a selection of organic materials plotted as a function
of the intermolecular interaction distance limit. These
data show typical atom-atom summation distances and
demonstrate that materials exhibiting a range of dif-
ferent types of intermolecular bonding (including
hydrogen bonding) and different degrees of elec-
trostatic interactions can be simulated with confidence.
The suitability of the intermolecular potentials used is
also demonstrated by the comparison of the calculated
lattice energy to the experimental lattice energy (Vex,)
shown in table 3. This latter quantity is obtained from
the experimentally determined sublimation enthalpy
(AHsuJ via
Vex, =-AH,,b - 2RT
( 8)
where 2RT represents a correction factor for the dif-
ference between the gas phase enthalpy and the
vibrational contribution to the crystal enthalpy (Wil-
liams 1966).
0
(0011
10021
I
e
Figure 4. Morphologies of a-sulphur: (a), ( b) commonly
observed forms; (c) theoretical prediction with no extinction
conditions applied; (d) theoretical prediction with lattice
centring only considered; (e) theoretical prediction with all
extinction conditions applied.
Table 1. Relative morphological importances for a-sulphur
using the BFOH model with and without extinction conditions
applied.
No Face-centring
conditions Face centring +glide planes Observed
space group P2,/a in a bimolecular unit cell of dimen-
sions a =8.098, b =5.953 and c =8.652 8, and B =
124.4 (Ponomarev et al 1976). The forms likely to
dominate the crystal habit were identified using the
BFDH model and are listed in table 2. The observed
morphology is shown in figure 5( a) and the computed
BFDH morphology in figure 5(b).
3.2.2. Benzoic acid. Benzoic acid (C6H5C0,H) is an
aromatic carboxylic acid which crystallizes in the mon-
oclinic space group P2,/c with four molecules in a unit
cell of dimensions a=5.510, b -5.157 and c =
21.973 8, with p =97.41 (Bruno and Randaccio 1980).
The results from the BFDH and attachment energy
calculations are listed in table 4. The intermolecular
bonds were calculated using the parameter set of Lifson
et a1 (1979). The observed morphology for benzoic
acid, taken from Groth (1906) and Berkovitch-Yellin
(1985), and given in figure 7(a) shows a (001) main face
with smaller loll}, {loo} and {lo?} side faces. The BFDH
model of the morphology (figure 7(b)) has all these
faces present in the prediction but is considerably
thicker along the c axis and has additional {110}and
{Til} forms present. The AE model of the morphology
(figure 7(c)) is in closer agreement with the observed
form. It is not as thick along the c axis as the BFDH
model and has no extra faces present. The only dif-
ferences between the observed morphology and the AE
model are the overestimation of the {loo} form and the
underestimation of the {lo?} form.
3.2.3. Hexamine. Hexamine (hexamethylenetetra-
mine, urotropine. (cH),N,) crystallizes unusually for
an organic material in the highly symmetrical cubic
space group 143111 with two molecules in a body-centred
unit cell of side 7.0218, (Dickinson and Raymond
1923).
The results of the BFDH and attachment energy
(using parameters from Momany el al (1974)) cal-
culations are given in table 5 . The high multiplicity
(number of symmetry-equivalent faces) of the pre-
dicted forms is due to the high symmetry of the system
under study and indicates that a small number of forms
93
R Docherty et a/
Table 2. Interplanar spacings and attachment energy values for naphthalene showing the
F laces determined by Hartman (1973); the asterisk indicates ObSeNed forms.
Bonds contributing Eau 8"
to Eaut (HP model) (AE model)
Form
(hU
(001 1' 7.14 2f +49 -4.06 -5.96
{l l V 4.63 2d+ 2a +2f + 2g -10.41 -12.24
(20i7' 4.02 4d +2f -10.50 -13.07
(1101' 4.44 2d +2a +2g -9.35 -11.77
i20* 3.69 -15.34
(1 la 3.49 -14.31
@OI 3.34 44 +49 -12.44 -14.79
(111) 3.26 -14.25
iozoj 2.97 -17.46
~~ -
t The definition of Eau used in this study istwicethat of Hartman so for consistency
Hartman's values have been doubled. For the definition of a, d, f and g see figure 8.
Flgure 5. Morphologies 01 naphthalene: ( a) observed
morphology; (b) BFDH model: (c) AE model; (4 IS model; (e)
Hartman-Perdok model.
dominates the crystal habit. The observed morphology
is a rhombic dodecahedron dominated by (110) forms.
Both the BFDH and AE models also exhibit this type of
morphology.
94
3.2.4 Naphthalene. The intermolecular forces were cal-
culated for naphthalene using parameters from Wil-
liams (1966) and the attachment energies for the forms
predicted from the BFDH model are tabulated in table
2. The corresponding computed morphology is shown
in figure 5(c).
3.3. ki ng model
'The ljing model crystal moiphoiogy ..vas dctcrmincd
using the intermolecular bond strengths used in the AE
model analysis outlined in section 3.2.4. Figure 8 shows
the unit cell, important bond types and the calculated
bond energies.
The connected and corresponding rectangular nets
for the (OOl ), (ZOT), (110) and (117) faces are shown in
figures 9 and 10 respectively. The resulting calculated
critical Ising temperature OC for each face is given in
table 6 and assuming the growth rate to be proportional
to l /W the king morphological simulation is given in
the Wulff plot shown in figure 5( d ) .
4. Discussion and comparison of models
In the examples studied in the previous section the AE
models of the crystal morphology generally give a bet-
ter fit to the observed morphologies than the simple
BFDH models. The improvement is particularly appar-
ent in the case of benzoic acid where there is direc-
tionally strong hydrogen-bonding, but less apparent
in the cases of naphthalene and hexamine where the
bonding is more isotropic and dipole effects are less
important.
Results similar to those observed for benzoic acid
have heen found for biphenyl and succinic acid (Doch-
erty and Roberts 1988) where the difference between
AE and BFDH models is considerable, particularly for
succinic acid. This effect is not quite as strong in ben-
zoic acid as the hydrogen-bonding is held within
dimers, whereas in succinic acid the hydrogen-bonding
continues throughout the structure in one direction.
Structural models for morphological prediction
-40-
- -
I :
E
: -30
8
r_
-20
'y r -10
..
A
0 7
7
Table 3. Calculated lattice energies and 'experimental' lattice energies (based on sublimation
enthalpies fromCox and Pilchard (1970)) for a range of organic materials. The type of potential
used to calculate the intermolecular interactions isstated and referenced: [ l ] Williams 1966; 121
Momany et a/ 1974; 131Lifson et a/ 1979.
Lattice 'Experimental'
energy lattice energy Potential
Material (kcal mol-') (kcal mol-') function Reference
n-octadecane
Biphenyl
Naphthalene
Anthracene
Benzophenone
Trinitrotoluene
e-gl ycine
L-alanine
Benzoic acid
p-succinic acid
Urea
-35.2
-21.6
-19.4
-24.9
-24.5
-25.1
-33.0
-33.3
-20.4
-30.8
-22.7
-37.8
-20.7
-18.6
-26.2
-23.9
-24.4
-33.8
-34.2
-23.0
-30.l t
-22.2
Buckingham
Buckingham
Buckingham
Buckingham
Lennard-J ones
Lennard-J ones
Lennard-J ones
Lennard-J ones
Lennard-J ones
Lennard-Jones
Lennard-Jones
t FromMomany et a/ (1974)
Table 4. Interplanar spacings and anachment energies for
benzoic acid; the asterisk indicates ObSeNed forms.
Eau
(kcal mol-')
Form
Wl)
{oozy 10.89 -3.1
(100)' 5.46 -6.5
(l Oz). 5.16 -6.5
( o i l y 5.02 -13.8
4.66 -13.8
4.65 -14.5
(012)
H021
io14 4.20 -13.1
4.13 -7.8
3.75 -16.7
(1 m
3.75 -16.7
m1I
(110)
Even though the BFDH model does not give as good
a fit as the AE models the BFDH approach can be used
to identify the important forms for refinement through
energy calculations. This procedure allows the energy
calculations to be concentrated on the most important
forms.
For naphthalene the growth morphology (figure
5(a)) is dominated by the {OOl} flat main face with {110}
and {lli} side faces and {207} and {101} front faces
(Pavlovska and Nenow 1972). The BFDH, AE and IS
models (figures 5(b)-(d), respectively) all show the
{OOl} forms as the most important. The BFDH and AE
models have the {llO) and {llx) side faces and the
(207) front face and agree well with the observed mor-
phology. The BFDH model shows an additional
{203} form. The IS model shows all the main forms
except for {lli}. Clearly the {l l O} and (114 forms
are competing, developing in the same zone and so
underestimates or overestimates in either can result in
the absence of one and dominance of the other.
Previous calculations of attachment energies for
naphthalene were carried out by Hartman (1973) using
the classical Hartman-Perdok (HP) method which is
similar to the AE model but typically only considers
bonding in the first coordination sphere. Hartman's
PBC analysis proposed five F faces and four important
intermolecular interactions. The value of the attach-
ment energy of each face was expressed in terms of
these bonds (see table 2) . The attachment energies for
95
R Docherty et a/
10011
I
I l O i l (1001
b
10011
(0 111
f j j Y
- - - - - - - - - - - - - -
I 1021 I 1001
Figure 7. Morphologies of benzoic acid: (a) observed
morphology; (b) BFDH model; ( C) AE model.
Table 5. lnterp anar spacings ana attachment energy
ca culations for nexamine. the asterak indicates observed
lorms
Form
{hkl) $ mol-') Multiplicity
(1 10)' 4.96 -8.36 12
(2001 3.51 -11.86 6
(2111 2.87 -11.95 24
Table 6. Calculated dimensionless critical king
temperatures, Bc, for naphthalene.
10011 3.22
i2oij 1.54
(1101 2.59
il ooi 0.92
I t m 1.36
the F faces were evaluated using the intermolecular
bond strengths given in figure 8 and the resulting HP
model of the morphology shown in figure 5(e). A com-
parison between the AE and HP calculated attachment
96
L
Figure 0. Important intermolecular interactions in the
naphthalene unit cell, a,= -1.56, d= -2.36, g = -0.75,
f =-0.53 kcal mol-'.
(0011
0
( 20i )
b
I1101
c
d
Figure 9. Connected nets for the most important faces in
the naphthalene morphology: (a) the (009 face: (b) the
(207) face: (c) the (1 10) face; (d) the (1 11) face. a, d, f and
g are the important intermolecular interactions shown in
figure 8.
energies is given in table 2. The AE model appears to
predict larger attachment energies than the HP model.
This is probably due to the former including more
intermolecular interactions than the latter model which
considers only strong nearest-neighhour interactions.
However, Hartman's HP analysis is useful in that
we can directly compare it with the Ising model which
also considers only near-neighbour interactions. The
HP model of naphthalene shows a much better agree-
ment with the observed morphology than does the IS
model. This is probably due to the fact that the IS
model reflects the stable crystal morphology close to
the growth conditions for kinetic roughening. At low
supersaturations additional less stable faces may grow
without significant roughening and in this case the AE
Structural models for morphological prediction
1001)
0
@ 0 9
I Z O i l
b
I1101
c
ciiii
d
Figure 10. Rectangular nets for the most impoltant faces
in the naphthalene morphology: ( a) the (col) face; (b) the
(201) face; (c) the (110) face; (d) the (111) face.
and HP models provide a more realistic simulation of
the expected morphology. Nevertheless this IS simu-
lation provides many useful clues as to the face-specific
nature of growth during kinetic roughening.
5. Conclusions
In this paper we have overviewed the models that have
been developed for the routine simulation of crystal
morphology on the basis of crystal structure. Computer
programs for the kind of simulations described here
are available in the public domain (see Docherty er al
1990) and the calculations outlined here can safely he
described as routine. Research in our groups (e.g.
Docherty 1989) and others worldwide (e.g. Addadi er
al 1986, van der Voort 1990) is currently devoted to
understanding the many additional factors such as sol-
vent, polymorphism, 'tailor-made' additives, confor-
mational flexibility, chirality, polar morphology etc
which play a role in further refining our capability to
predict and understand the morphology of molecular
crystals.
Acknowledgments
Research on morphological modelling has been sup-
ported for a number of years through collaborative
programmes involving the SERC, Exxon Chemicals
and IC1 Chemicals and Polymers. We gratefully
acknowledge these agencies for financial support and
wish also to thank S N Black, R J Davey, K Lewtas
and R D Tack for their interest in this work. One
of us (CC) gratefully acknowledges Exxon/SERC for
financial support.
Appendices
A. l . Shape
SHAPE is a crystal drawing program written by Dowty
(1980). It uses the classical Wulff plot of the equi-
librium form as described in section 2.1. It requires
information such as unit cell dimensions, space-group
symmetry and centre-to-face distances and computes
the smallest polyhedron enclosed by the faces to pro-
duce a picture of the crystal.
If observed centre-to-face distances are used then
a picture of the observed morphology is the result. If
the reciprocal of the interplanar spacing is used then
the BFDH model of the morphology results. When
attachment energies are used then the AE model of the
morphology results. If reciprocals of the critical king
temperatures are used then the IS model of the mor-
phology results.
A.2. MORANG
MORANG is a highly interactive, user-friendly package
designed to aid in determining crystal morphology. The
program is written in standard FORTRAN-77 and consists
of three main functions:
(i) The identification of the most important mor-
phological forms according to interplanar spacings.
This is essentially the BFDH approach detailed in section
2.2.
(ii) The calculation of the angles between crystal
planes and directions.
(iii) Using a combination of the above options the
user can input an observed angle plus experimental
error and the program will output the likely planes.
This allows the identification of the forms present in
the crystal habit.
MORANG has been described in some detail (Doch-
erty er al 1988) and can be run on any machine which
supports standard FORTRAN-77. It is available from the
Computer Physics Communications (CPC) program
library.
A.3. HABIT
HABIT is a FORTRAN program designed to calculate
lattice, slice and attachment energies in order to predict
the morphology of molecular crystals using the attach-
ment energies as a measure of relative growth rate. It
uses the fractional coordinates of one asymmetric unit
and the symmetry operators for the appropriate space
97
R Docherly et a/
group to construct the unit cell. Repeated generation
of this unit cell along the crystal directions U, V and
W creates a three-dimensional model of the crystal.
The intermolecular interactions are considered to con-
sist of the sum of all the atom-atom interactions. Each
atom-atom interaction is assumed to have a van der
Waals and an electrostatic part.
HABIT outputs the lattice, slice and attachment ener-
gies through selective summation of molecular inter-
actions and these allow morphological predictions to
he carried out. The program has been described in
detail (Clydesdale et a1 1990) and is available from the
CPC library.
A.4. CRYSTLINK
CRYSTLINK (Clydesdale, Docherty and Roberts, unpuh-
lished) was written as a support program and contains
a series of useful routines which carry out a variety of
data manipulation procedures. The program is written
in FORTRAN and runs on the VAX series of computers
(e.g. 11/782, 6330). The program uses some of the
mathematical routines available in the NAG library
and as a result the program requires linking to this
library. The program could easily be modified to run on
other machines with slight changes to the file handling
options which are specific to the VAX. Some of the
routines avaiiabie are deiaiied beiow.
A starting file of atomic coordinates obtained from
the CSSR database (CSE Applications Group, Darcs-
bury Laboratory), a version of the Cambridge Struc-
tural Database, can be used to generate partial or
complete files for a variety of programs including HABIT
and various quantum mechanical and molecular gra-
phics packages.
Molecular graphics routines work in Cartesian coor-
dinates. When considering crystal systems it is con-
ventional to deal in crystal coordinates which are
expressed as fractions of the unit cell. CRYSTLINK allows
the interconversion of the two coordinate systems. This
is useful when fitting hydrogens to incomplete struc-
tures.
Given a standard CSSR file and a list of symmetry
operators for the appropriate space group CRYSTLINK
will prepare files containing information for displaying
crystal packing diagrams and slice diagrams.
Details of this program are available from the
authors on request.
AS . TCCALC
TCCALC is a program developed by Rijpkema (1984)
which allows the calculation of the critical king tem-
perature 0' from a rectangular net given a ratio of
bond energies. It uses Onsager's analytical solution to
calculate the critical temperature for a two-dimensional
king net. The procedure for obtaining bond energies
and rectangular nets is discussed for naphthalene in
section 3.3.
98
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