BIOGRAPHICAL DETAILS
Mark Spackman received his BSc in chemical physics (1976)
and PhD in theoretical chemistry (1980) from the University of
Western Australia. After several years of postdoctoral studies
he was appointed at the University of New England in 1987.
Promoted to Professor in 1999, he has served terms as Convenor
of Chemistry and Head of School at the University of New
England. In 2003 he was awarded a five-year ARC Australian
Professorial Fellowship (2004-2008), which will enable him to
focus full-time on his research for an extended period, and in
2004 he was appointed at the University of Western
Australia.
Professor Spackman is active in a national and international
professional capacity. He has been Secretary (1995-1997) and
President (2001-2003) of the Society of Crystallographers in
Australia & New Zealand, a member of the Australian Academy
of Science National Committee for Crystallography, and was a
past member (1993-1998) and Chair (1999-2002) of the
International Union of Crystallography Commission on Charge,
Spin and Momentum Densities. He recently completed a two-year
term as a member of the Australian Research Council Expert
Advisory Committee on Physics, Chemistry and Geoscience.
Professor Spackman has delivered numerous invited research
lectures at recent international conferences. In 2003 he
delivered a keynote lecture at the 16th International
Conference on the Chemistry of the Organic Solid State,
and in 2004 was an invited speaker and instructor at the
35th Erice Crystallography School. In 2005 he has been
invited to deliver a keynote lecture at the 20th Congress
and General Assembly of the International Union of
Crystallography, to be held in Florence in August.
RESEARCH INTERESTS
Research in the group is broadly focused on bridging the gap
between theoretical and experimental determinations of
molecular properties, and the use of tools and methods from
computational chemistry to inform aspects of modern
crystallography, especially crystal packing. The interaction
with (and critical assessment of) experimental data and results
is always a significant component of this research. Active
projects currently span two main areas: (i) the extraction of
physical and chemical information (especially molecular dipole
moments, electric field gradients at nuclei, intermolecular
interaction energies and, most recently, nonlinear optical
(NLO) properties) from accurate X-ray diffraction data, and:
(ii) the exploration and exploitation of a novel scheme devised
recently for partitioning crystal space into molecular
fragments - so-called Hirshfeld surfaces.
The X-ray diffraction project has to date used model
structure factors for molecules and crystals to calibrate the
extraction of properties such as dipole and quadrupole moments,
electric fields and electric field gradients at the nuclei, and
even electrostatic intermolecular interaction energies, from
the diffraction data. The outcomes are of considerable
significance as single-crystal X-ray data is increasingly more
accurate and precise, and the potential for it to yield more
than just atomic positions and thermal ellipsoids is now widely
recognised, but not yet realised in any routine fashion. This
work has attracted previous funding from the Australian
Research Council (1994-96 and 1997-99), and several recent
publications [42, 44, 46, 56, 57] exemplify the outcomes from
this project to date.
More recently, ARC funding has been awarded (2004-2008) for
a project involving estimation of nonlinear optical (NLO)
properties of important NLO organic molecular crystals from
X-ray diffraction data. This project will develop and implement
innovative approaches in the charge density analysis of
high-resolution, low-temperature single-crystal X-ray
diffraction data, to obtain in-crystal estimates of the
electronic part of molecular (hyper)polarisabilities and
related bulk susceptibilities. The program will exploit
advances in CCD technology for X-ray data collection,
procedures for electron density and wavefunction fitting, and
analysis of molecular dynamics in crystals.
Recent work investigating applications of the Hirshfeld
surface in molecular crystals is closely connected with crystal
engineering. Crystal engineering seeks to better understand the
interactions between molecules in terms of their packing in
crystals, for use in the ultimate design of new solids with
desirable physical and chemical properties. By partitioning
crystals into smooth, non-overlapping molecular (Hirshfeld)
surfaces, this research is investigating completely novel ways
to extract the extraordinary amount of information on
intermolecular interactions which crystal structures contain,
in a format which is more readily assimilated, and which sheds
new light on the subtle interplay between the interactions
responsible for forming molecular crystals.
  Our initial report [45]
on these fascinating surfaces appeared in 1997, and presented
some preliminary results using the Hirshfeld surface to
integrate electron densities for urea, ice VIII and formamide.
An early summary of applications to crystal engineering
appeared in Chemistry - A European Journal [47], and
was featured on the cover of that issue. A subsequent short
communication highlighted the dramatic way in which the
Hirshfeld surface conveys information on different types of
intermolecular interactions, with application to naphthalene
and terephthalic acid [49]. That work also explored the
relationship between the Hirshfeld surfaces and conventional
fused-sphere and ab initio electron density molecular surfaces.
More recently, we have been pursuing the colour mapping of
properties (e.g. distance from the surface to the nearest atom
outside the surface, and functions of curvature) on the
Hirshfeld surface. This has been done with two initial
objectives in mind: constructing a pictorial glossary of
intermolecular interactions, and exploring its application to
polymorphic molecular crystals. Hirshfeld surfaces decorated in
this manner are spectacularly successful at conveying the
subtle details only hinted at earlier, but there is a problem:
3D colour graphics are essential to the task. To overcome this
we have devised fingerprint plots which summarise
intermolecular contacts in a convenient 2D format; see the
recent paper in CrystEngComm [58] for more details and
a myriad of examples. Further artwork on Hirshfeld surfaces
featured on the cover of Acta Crystallographica B in
2004, accompanying a major paper describing in detail the
application of these tools to a wide range of molecular crystal
structures [62]. The reader is also referred to our web
site for up to date results from this exciting
work.
RECENT PUBLICATIONS[63] Spackman, M.A., Jiang, B., Groy, T.L., He, H., Whitten, A.E. & Spence, J.C.H., Phase measurement for accurate mapping of chemical bonds in acentric space groups, Physical Review Letters, (2004) 95, 085502.
[62] McKinnon, J.J., Spackman, M.A. and
Mitchell, A.S., Novel tools for visualizing and
exploring intermolecular interactions in molecular crystals,
Acta Cryst. B60 (2004) 60,
627-668.
[61] Whitten, A.E., Dittrich, B.,
Spackman, M.A., Turner, P. and Brown, T.C., Charge
density analysis of two polymorphs of antimony(III) oxide,
Dalton Trans., (2004) 23-29.
[60] Gibbs, G.V., Whitten, A.E.,
Spackman, M.A., Stimpfl, M., Downs, R.T. and Carducci,
M.D., An exploration of theoretical and experimental
electron density distributions and SiO bonded interactions for
the silica polymorph coesite, J. Phys. Chem.
B (2003) 107, 12996-13006.
[59] Spackman, M.A., From charge
densities to crystal engineering, Z.
Kristallogr., (2002) 217, 369-370.
[58] Spackman, M.A. and McKinnon,
J.J., Fingerprinting intermolecular interactions in
molecular crystals, CrystEngComm,
(2002) 4, 378-392.
[57] Brgi, H.B., Capelli, S.C., Goeta,
A.E., Howard, J.A.K., Spackman, M.A. and Yufit, D.S.,
Electron distribution and molecular motion in crystalline
benzene. An accurate experimental study combining CCD X-ray
data on C6H6 with multi-temperature neutron diffraction results
on C6D6, Chem. Eur. J., (2002) 8,
3512-3521.
[56] Spackman, M.A. and Mitchell,
A.S., Basis set choice and basis set superposition error
(BSSE) in periodic Hartree-Fock calculations on molecular
crystals, Phys. Chem. Chem. Phys.,
(2001) 3, 1518-1523.
[55] Russell, A.J. and Spackman,
M.A., An ab initio study of vibrational corrections to
the electrical properties of ethane, Mol.
Phys., (2000) 98, 867-874.
[54] Russell, A.J. and Spackman,
M.A., An ab initio study of vibrational corrections to
the electrical properties of ethylene, Mol.
Phys. (2000) 98, 855-865.
[53] Russell, A.J. and Spackman,
M.A., An ab initio study of vibrational corrections to
the electrical properties of the fluoromethanes: CH3F, CH2F2,
CHF3 and CF4, Mol. Phys. (2000) 98,
633-642.
[52] Russell, A.J. and Spackman,
M.A., Contracted basis sets for electrical property
calculations derived from MP2 atomic natural orbitals, Theor. Chem. Acc. (2000) 104, 385-391.
[51] Mitchell, A.S. and Spackman,
M.A., Molecular surfaces from the promolecule. A
comparison with Hartree-Fock ab initio electron density
surfaces, J. Comp. Chem. (2000) 21,
933-942.
[50] Spackman, M.A., Hydrogen
bond energetics from topological analysis of experimental
electron densities: Recognising the importance of the
promolecule, Chem. Phys. Lett. (1999)
301, 425-429.
[49] McKinnon, J.J., Mitchell, A.S. and
Spackman, M.A. Visualising intermolecular interactions
in crystals: naphthalene vs. terephthalic acid, Chem.Commun. (1998) 2071-2072.
[48] Spackman, M.A., Charge
densities from X-ray diffraction data, Ann.
Rep. Prog. Chem., Sect. C: Phys. Chem. (1998) 94,
177-207.
[47] McKinnon, J.J., Mitchell, A.S. and
Spackman, M.A., Hirshfeld surfaces: A new tool for
visualising and exploring molecular crystals, Chem. Eur. J. (1998) 4, 2136-2141.
[46] Spackman, M.A., Byrom, P.G.,
Alfredsson, M. and Hermansson, K.G., Influence of
intermolecular interactions on multipole-refined electron
densities, Acta Cryst. (1999) A55,
30-47.
[45] Spackman, M.A. and Byrom,
P.G., A novel definition of a molecule in a crystal,
Chem. Phys. Lett. (1997) 267,
215-220.
[44] Spackman, M.A. and Byrom,
P.G., Retrieval of structure factor phases in
noncentrosymmetric space groups. Model studies using multipole
refinements, Acta Cryst. (1997) B53,
553-564.
[43] Russell, A.J. and Spackman,
M.A., An ab initio study of vibrational corrections to
the electrical properties of the second-row hydrides, Mol. Phys. (1997) 90, 251-264.
SELECTED PUBLICATIONS BEFORE 1997
Spackman, M.A.
"Potential-derived charges using a geodesic point selection
method", J. Comp. Chem., 17, 1-18,
1996.
Spackman, M.A. "Molecular
electric moments from x-ray diffractions data", Chem. Rev. 92, 1769-1797, 1992.
Spackman, M.A., Weber, H.-P. and
Craven,B.M. "Energies of molecular interactions from
Bragg diffraction data", J. Am. Chem. Soc.
110, 775-782, 1988
Spackman, M.A. "Atom-atom
potentials via electron gas theory", J. Chem.
Phys. 85, 6579-6586, 1986.
Spackman, M.A. "A simple
quantitative model of hydrogen bonding", J.
Chem. Phys. 85, 6587-6601, 1986.
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