Repulsion Dispersion Potentials
Most of the crystal structure modelling using DMAREL & DMACRYS
that has not derived a specific potential for the molecule1,2
has supplemented the Distributed Multipole electrostatic model with
an empirically fitted isotropic atom-atom potential of the form:
where atom i of type i in molecule
M is separated by Rik from atom k of type k
in molecule N. Some notes and comments on their use follow, with references
to the definitive literature.
WILL01 was derived3 by fitting to a wide range of
crystal structures and validated against peptide and nucleoside structures.
A key feature is that the hydrogen interaction sites are moved by 0.1
Å into the H-X bond from their neutron or ab initio optimised positions.
DMACRYS can perform this foreshortening, which has to also be used in
the DMA analysis.
Potential |
Atom pair |
Description |
Aik /kJ mol-1 |
Bik/Å-1 |
Cik/kJ mol-1
Å6 |
WILL01 |
C(2)···C(2) |
C bonded to 2 atoms |
103235 |
3.60 |
1435.09 |
WILL01 |
C(3)···C(3) |
C bonded to 3 atoms |
270363 |
3.60 |
1701.73 |
WILL01 |
C(4)···C(4) |
C bonded to 4 atoms |
131571 |
3.60 |
978.36 |
WILL01 |
H(1)···H(1) |
H bonded to C |
12680 |
3.56 |
278.37 |
WILL01 |
H(2)···H(2) |
H in alcoholic group |
361.30 |
3.56 |
0 |
WILL01 |
H(3)···H(3) |
H in carboxyl group |
115.70 |
3.56 |
0 |
WILL01 |
H(4)···H(4) |
H in N-H group |
764.90 |
3.56 |
0 |
WILL01 |
N(1)···N(1) |
N in triple bond |
96349 |
3.48 |
1407.57 |
WILL01 |
N(2)···N(2) |
other N with no bonded H |
102369 |
3.48 |
1398.15 |
WILL01 |
N(3)···N(3) |
N bonded to 1 H atom |
191935 |
3.48 |
2376.55 |
WILL01 |
N(4)···N(4) |
N with 2 bonded H atoms |
405341 |
3.48 |
5629.82 |
WILL01 |
O(1)···O(1) |
O bonded to 1 other atom |
241042 |
3.96 |
1260.73 |
WILL01 |
O(2)···O(2) |
O bonded to 2 other atoms |
284623 |
3.96 |
1285.87 |
This potential was successfully used in a large survey of crystal structure
predictions in conjunction with both a point charge4 and
Distributed Multipole model5. However problems have been
observed in underestimating hydrogen bond distances when combined with
a Distributed Multipole Model, presumably because the electrostatic
forces can be stronger than with the point charge model used in Williams'
parameterisation. In certain cases, of (carboxylate)O···H-O
and N···H-O hydrogen bonds the underestimate has
led to the hydrogen bonds becoming within the covalent bond range. (An
ad hoc fix for the latter6 is to replace the purely repulsive,
Williams potential between pyridine nitrogen and carboxylic proton (N(2).H(3))
to A=75719.47 kJ/mol and B=5.1765 Å-1 to model the cocrystal
of 4-aminobenzoic acid with 4-nitrophenylacetic acid. This potential
is much steeper at unphysically short distances without penalising the
lattice energy at typical contacts compared with the original Williams
parameterisation.) Graeme Day's group noted noted that O-H(3)···N(2)
distances were unreasonably short for the cocrystal in the 2007 blindtest,
and found substituting the alcohol H(2) parameters for H(3) in this
carboxylic acid produced more reasonable results. We are currently testing
the published WILL01 potentials for a range of systems, to establish
whether it is worth providing a revision of all the polar hydrogen parameters
for use in conjunction with a DMA.
FIT has evolved through using Williams older parameterisations,
which had each element in conjunction with C and H only. The H nuclei
are used as the interaction sites, although whether Williams corrected
for the X-ray foreshortening in these derivations is unclear.
Reference |
Atom pair |
Description |
Aik /kJ mol-1 |
Bik/Å-1 |
Cik/kJ mol-1
Å6 |
7 |
C···C |
Any C atom |
369743 |
3.60 |
2439.8 |
7 |
H···H |
H bonded to C |
11971 |
3.74 |
136.4 |
8 |
HN···HN |
H bonded to N |
5029.68 |
4.66 |
21.50 |
9 |
HO···HO |
H bonded to O |
2263.3 |
4.66 |
21.50 |
7 |
N···N |
Any N atom |
254529 |
3.78 |
1378.4 |
10 |
O···O |
Any O atom |
230064.1 |
c=3.96 |
1123.59 |
11 |
F···F |
Any F atom |
363725 |
4.16 |
844 |
12 |
Cl···Cl |
Any Cl Atom |
924675 |
c=3.51 |
7740.48 |
Other parameters that have been used in conjunction
with FIT for a few applications |
16 |
S···S |
S atoms in blind tests (for thiol and thioether) |
401033.7336 |
3.30 |
5790.656 |
17 |
S···S |
S atoms in sulfoxides |
236501.5221 |
2.90 |
8397.1147 |
17 |
O···O |
O atoms in sulfoxides |
202983.6471 |
3.96 |
640.8628309 |
Note that NEIGHBOURS does not distinguish between H-O and H-N and so
many papers have use the HN (=Hp) parameters for
any polar hydrogen, including in hydrates and ice.13 NEIGHCRYS
will automatically provide the Williams typing and can allow a user
specified typing, allowing the ability of DMACRYS to use more atomic
types for a given atom to be applied without manual editing of the input
file. The extent to which the parameters in combination have been tested
beyond8 is limited, though there has been some validation
for the F parameters in Ashley Hulme's thesis and for the isotropic
chlorine in situations without close Cl···Cl contacts.14
There are various failures: problems in stacking of some rigid aromatics
differences led Tom Lewis to reduce the C parameters by 25% in his studies
(thesis + 15 ).
It is important to note that both these empirically fitted potentials
are effectively modelling the total intermolecular potential with the
electrostatic component removed, as well as it is sampled in the crystal
structures used for fitting and validation. It is not surprising that
the results can be sensitive to the quality of the electrostatic model
used, and may be very poor for atypical short contacts. Since they are
empirically based, the choice of which to use can only be made by empirical
testing for related crystal structures.
Reference List
- Price SL, Price LS 2005. Modelling Intermolecular Forces for Organic
Crystal Structure Prediction. In Wales DJ, editor. Intermolecular Forces
and Clusters I, Berlin, Heidelberg, Germany: Springer-Verlag. p 81-123.
- Price SL 2004. Quantifying intermolecular interactions and their use
in computational crystal structure prediction. CrystEngComm 6:344-353.
- Williams DE 2001. Improved intermolecular force field for molecules
containing H, C, N, and O atoms, with application to nucleoside and
peptide crystals. J Comput Chem 22:1154-1166.
- Day GM, Chisholm J, Shan N, Motherwell WDS, Jones W 2004. Assessment
of lattice energy minimization for the prediction of molecular organic
crystal structures. Cryst Growth Des 4:1327-1340.
- Day GM, Motherwell WDS, Jones W 2005. Beyond the isotropic atom model
in crystal structure prediction of rigid molecules: Atomic multipoles
versus point charges. Cryst Growth Des 5:1023-1033.
- Karamertzanis PG 2008. CoCrystal prediction DMAflex. Cryst Growth
Des in preparation.
- Williams DE, Cox SR 1984. Nonbonded Potentials For Azahydrocarbons:
the Importance of the Coulombic Interaction. Acta Crystallogr , Sect
B 40:404-417.
- Coombes DS, Price SL, Willock DJ, Leslie M 1996. Role of Electrostatic
Interactions in Determining the Crystal Structures of Polar Organic
Molecules. A Distributed Multipole Study. J Phys Chem 100:7352-7360.
- Beyer T, Price SL 2000. Dimer or catemer? Low-energy crystal packings
for small carboxylic acids. J Phys Chem B 104:2647-2655.
- Cox SR, Hsu LY, Williams DE 1981. Nonbonded Potential Function Models
for Crystalline Oxohydrocarbons. Acta Crystallogr , Sect A 37:293-301.
- Williams DE, Houpt DJ 1986. Fluorine Nonbonded Potential Parameters
Derived From Crystalline Perfluorocarbons. Acta Crystallogr , Sect B
42:286-295.
- Hsu LY, Williams DE 1980. Intermolecular Potential-Function Models
for Crystalline Perchlorohydrocarbons. Acta Crystallogr , Sect A 36:277-281.
- Hulme AT, Price SL 2007. Towards the prediction of organic hydrate
crystal structures. J Chem Theory Comput 3:1597-1608.
- Barnett SA, Johnson A, Florence AJ, Price SL, Tocher DA 2008. A systematic
experimental and theoretical study of the crystalline state of six chloronitrobenzenes.
Cryst Growth Des 8:24-36.
- Lewis TC, Tocher DA, Price SL 2005. Investigating Unused Hydrogen
Bond Acceptors Using Known and Hypothetical Crystal Polymorphism. Cryst
Growth Des 5:983-993.
- Lommerse JPM, Motherwell WDS, Ammon HL, Dunitz JD, Gavezzotti A, Hofmann DWM, Leusen FJJ, Mooij WTM, Price SL, Schweizer B, Schmidt MU, van Eijck BP, Verwer P, Williams DE 2000. A test of crystal structure prediction of small organic molecules. Acta Crystallogr, Sect B 56:697-714; Halgren TA 1992. Representation of Vanderwaals (Vdw) Interactions in Molecular Mechanics Force-Fields - Potential Form, Combination Rules, and Vdw Parameters. J Am Chem Soc 114:7827-7843.
- "Table Sheraga" in Supporting Information of Motherwell WDS, Ammon HL, Dunitz JD, Dzyabchenko A, Erk P, Gavezzotti A, Hofmann DWM, Leusen FJJ, Lommerse JPM, Mooij WTM, et al. 2002. Crystal structure prediction of small organic molecules: a second blind test. Acta Crystallogr, Sect B 58:647-661
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