W/Prof Mark Spackman
Head of School/Winthrop Professor
School of Chemistry and Biochemistry
- Contact details
- School of Chemistry and Biochemistry
The University of Western Australia (M310)
35 Stirling Highway
CRAWLEY WA 6009
- 6488 4699 / 6488 3140
- 6488 7330
- Room 411, Bayliss Building, Crawley campus
- BSc PhD W.Aust., FRACI
- 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), enabling 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 (1994-2004, 2008-2011), 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 has also served as a member of the Australian Research Council Expert Advisory Committee on Physics, Chemistry and Geoscience (2002-2003) and is currently a Co-Editor of Acta Crystallographica Section B.
Professor Spackman has delivered numerous invited research lectures at recent international conferences: 20th Congress and General Assembly of the IUCr, Florence, Italy (2005); meeting of the British Crystallographic Association, Lancaster, UK (2006); Gordon Research Conference on Electron Distributions and Chemical Bonding, Massachusetts, USA (2007); ECDMV - 5th European Charge Density Meeting, Gravedona, Italy (2008); 21st Congress and General Assembly of the IUCr, Osaka, Japan (2008).
- Key research
- Research Objectives:
- My current research focuses on three main areas, two of which attempt to bridge the gap between experimental and theoretical determination of molecular and crystalline properties, and the third somewhat more recent, springing from a rather novel observation made in the course of earlier research.
- Electric and optical properties of molecules and crystals:
- My major research interest for some years has been the extraction of electric properties of molecules and crystals from X‐ray diffraction data. Funded by ARC Large Grants over the years 1994‐1999 which have supported postdoctoral research fellows, this work was the subject of an earlier major review article in Chemical Reviews. That work used purely theoretical methods to ascertain the limitations on the multipole refinement methods presently used for the extraction of properties such as molecular moments, electric field gradients and intermolecular interaction energies from X‐ray data. More recently, this work has been extended to estimate linear and nonlinear optical properties of molecules from X‐ray diffraction data, and this was the subject of an ARC Discovery‐ Project grant for the years 2004‐2008.
- Vibrational averaging of molecular properties:
- Throughout the 1990s my secondary research interest was the accurate prediction of electric properties of molecules using ab initio computational techniques. The aim of the most recent work was to arrive at a routine method for the determination of the effects of rotational and vibrational motion on these properties. Until very recently the computation of these effects had only been performed for diatomic molecules, but we have demonstrated that it can be done in a relatively straightforward manner for polyatomic molecules. This work was funded by ARC Small Grants.
- Hirshfeld surface analysis and CrystalExplorer:
- The most recent thread in my research explores the use of a novel scheme for partitioning crystal space into molecular and atomic (ionic) volumes. This partitioning offers a completely new and hitherto unseen picture of atoms, ions and molecules in a crystalline environment, and the surfaces which result (we have named them Hirshfeld surfaces after the originator of the partitioning scheme we have adapted) appear to reflect the nature and strength of interatomic and intermolecular interactions in a quantitative manner. Twenty three papers on this exciting work have so far been published, seven of them accompanied by cover artwork in colour from our articles. Further applications and extensions of this work were the subject of a recent ARC Discovery‐Project grant (2005‐2007), and also comprise an important part of a new ARC Discovery‐Project grant (2009‐2011). The focus of this latest project is the mapping of voids and their properties in molecular crystals, as well as investigating a range of additional functions mapped on Hirshfeld surfaces, and derived from theoretical wavefunctions (e.g. local ionization energies, molecular orbital densities, and local electron affinities, functions which should provide information that complements that already available). The current interface of CrystalExplorer to the powerful Gaussian quantum chemistry package is opening up crystal engineering to a rigorous quantum chemical approach, and we intend to exploit this by incorporating the computation of intermolecular interaction energies into CrystalExplorer. This development will make the software powerful enough to not only routinely explore and visualize the patterns of interactions experienced by molecules in crystals, but also provide meaningful energies of interaction between relevant pairs of molecules. In this way researchers will be able to attach some real significance ‐ energetics ‐ to what has hitherto been simply a close contact, and for that reason assumed to be strongly attractive.
- Publications in last 5 years:
Nemkevich, A., Bürgi, H.B., Spackman, M.A., Corry, B., Molecular dynamics simulations of structure and dynamics of organic molecular crystals, Phys. Chem. Chem. Phys. (2010) accepted 10 September.
Skovsen, I., Christensen, M., Clausen, H.F., Overgaard, J., Spackman, M.A., Stiewe, C., Desgupta, T., Mueller, E., Iversen, B.B., Synthesis, crystal structure, atomic Hirshfeld surfaces and physical properties of hexagonal CeMnNi4, Inorg. Chem. (2010) DOI: 10.1021/ic100990a
Jiang, B., Zuo, J.M., Holec, D., Humphreys, C.J., Spackman, M.A., Spence, J.C.H., Structure-factor phase measurement for mapping of chemical bonds in GaN, Acta Cryst. (2010) A66, 446-450.
Dittrich, B., Bond, C.S., Kalinowski, R., Spackman, M.A., Jayatilaka, D., Revised electrostatics from invariom refinement of the 18-residue peptaibol antibiotic trichotoxin A50E
CrystEngComm (2010) 12, 2419-2423.
Clausen, H.F., Chevalier, M.S., Spackman, M.A., Iversen, B.B., Three new co-crystals of hydroquinone: crystal structures and Hirshfeld surface analysis of intermolecular interactions, New J. Chem. (2010) 34, 193-199.
Gandy, M.N., McIldowie, M.J., Skelton, B.W., Brotchie, J.M., Koutsantonis, G.A., Spackman, M.A., Piggott, M.J., Physical and crystallographic characterisation of the mGlu5 antagonist, MTEP, and its monohydrochloride, J. Pharm. Sci. (2010) 99, 234‐245.
Martin, A.D., Sobolev, A.N., Spackman, M.A., Raston, C.L., Variable intercalation of calcium ions in bilayers of partially deprotonated p‐phosphonic acid calixarene, Cryst. Growth Des. (2009) 9, 3759‐3764.
Poulsen, R.D., Overgaard, J, Schulman, A, Ostergaard, C, Murillo, C.A., Spackman, M.A., Iversen, B.B., Effects of weak intermolecular interactions on the molecular isomerism of tricobalt metal chains", J. Am. Chem. Soc. (2009) 131, 7580‐7591.
Harrowfield, J.M, Koutsantonis, G.A., Nealon, G.L., Skelton, B.W., Spackman, M.A., Proton switching of polarity in metalloamphiphile crystals, CrystEngComm (2009) 11,
Jayatilaka, D., Munshi, P., Turner, M.J., Howard, J.A.K., Spackman, M.A., Refractive indices for molecular crystals from the response of X-ray constrained Hartree-Fock wavefunctions, Phys. Chem. Phys. (2009) 11, 7209-7218.
Spackman, M.A., Jayatilaka, D., Hirshfeld surface analysis, CrystEngComm (2009) 11, 249-253.
Munshi, P., Madsen, A.Ø., Spackman, M.A., Larsen, S., Destro, R.. Estimated H-atom anisotropic displacement parameters: a comparison between different methods and with neutron diffraction results, Acta Cryst. (2008) A64, 465-475.
Wood, P.A.. McKinnon, J.J.. Parsons, S., Pidcock, E., Spackman, M.A., Analysis of the compression of molecular crystal structures using Hirshfeld surfaces, CrystEngComm (2008) 10, 368-376.
Spackman, M.A.. McKinnon, J.J.. Jayatilaka, D.. Electrostatic potentials mapped on Hirshfeld surfaces provide direct insight into intermolecular interactions in crystals, CrystEngComm (2008) 10, 377-388.
Munshi, P., Skelton, B.W., McKinnon, J.J., Spackman, M.A., Polymorphism in 3-methyl-4-methoxy-4’-nitrostilbene (MMONS), a highly active NLO material, CrystEngComm (2008) 10, 197-206.
Dittrich, B., Spackman M.A., Can the interaction density be measured? The example of the non-standard amino acid sarcosine, Acta Cryst. (2007) A63, 426-436.
Spackman, M.A., Munshi, P., Dittrich, B., Dipole moment enhancement in molecular crystals from X-ray diffraction data, ChemPhysChem (2007) 8, 2051-2063.
Spackman, M.A., Munshi, P., Jayatilaka, D., The use of dipole lattice sums to estimate dipole moment enhancement in molecular crystals, Chem. Phys. Lett. (2007) 443, 87-91.
McKinnon, J.J., Spackman, M.A., Jayatilaka, D., Towards quantitative analysis of intermolecular interactions with Hirshfeld surfaces, Chem. Commun. (2007) 3814-3816.
Fabbiani, F.P.A., Byrne, L.T., Spackman, M.A., McKinnon, J.J., Solvent inclusion in the structural voids of form II carbamazepine: single-crystal X-ray diffraction, NMR spectroscopy and Hirshfeld surface analysis, CrystEngComm (2007) 9, 728-731.
Dittrich, B., Munshi, P., Spackman, M.A., Re-determination, invariom model and multipole refinement of L-ornithine hydrochloride, Acta Cryst. (2007) B63, 505-509.
Clark, T.E., Makha, M., McKinnon, J.J., Sobolev, A.N., Spackman, M.A., Raston, C.L., Variable temperature Hirshfeld surface analysis of interdigitated calixarene bearing O-alkyl C18 linear chains, CrystEngComm (2007) 9, 566-569.
McKinnon, J.J., Fabbiani, F.P.A., Spackman, M.A., Comparison of polymorphic molecular crystal structures through Hirshfeld surface analysis, Cryst. Growth Des. (2007) 7, 755-769.
Parkin, A., Barr, G., Dong, W., Gilmore, C.J., Jayatilaka, D., McKinnon, J.J., Spackman, M.A., Wilson, C.C., Comparing entire crystal structures: Structural genetic fingerprinting, CrystEngComm (2007) 9, 648-652.
Spackman, M.A., Comment on the paper On the calculation of the electrostatic potential, electric field and electric field gradient from the aspherical pseudoatom model, by Volkov, King, Coppens & Farrugia (2006), Acta Cryst. (2007) A63, 198-200.
Gibbs, G.V., Cox, D.F., Rosso, K.M., Ross, N.L., Downs, R.T., Spackman, M.A., Theoretical electron density distributions for Fe- and Cu-sulfide earth materials: A connection between bond length, bond critical point properties, local energy densities, and bonded interactions, J. Phys. Chem. B (2007) 111, 1923-1931.
Makha, M., McKinnon, J.J., Sobolev, A.N., Spackman, M.A., Raston, C.L., Controlling the confinement and alignment of fullerene C¬70 in p-substituted calixarenes, Chem. Eur. J. (2007) 13, 3907-3912.
Whitten, A.E., Jayatilaka, D., Spackman, M.A., Effective molecular polarizabilities and crystal refractive indices estimated from X-ray diffraction data, J. Chem. Phys. (2006) 125, 174505.
Gibbs, G.V., Jayatilaka, D., Spackman, M.A., Cox, D.F., Rosso, K.M., Si-O bonded interactions in silicate crystals and molecules, J. Phys. Chem. A (2006) 110, 12678-12683.
Dittrich, B., Munshi, P., Spackman, M.A., Invariom-model refinement of L-valinol, Acta Cryst. (2006) C62, o633-o635.
Gibbs, G.V., Spackman, M.A., Jayatilaka, D., Rosso, K.M., Cox, D.F., Bond length and local energy density property connections for non-transition metal oxide-bonded interactions, J. Phys. Chem. A (2006) 110, 12259-12266.
Dittrich, B., Hübschle, C.B., Luger, P., Spackman, M.A., Introduction and validation of an invariom database for amino acid, peptide and protein molecules, Acta Cryst. (2006) D62, 1325-1335.
Whitten, A.E., Turner, P., Klooster, W.T., Piltz, R.O., Spackman, M.A., Re-assessment of large dipole moment enhancements in crystals: A detailed experimental and theoretical charge density analysis of 2-methyl-4-nitroaniline, J. Phys. Chem. A (2006) 110, 8763-8776.
Whitten, A.E., Spackman, M.A., Anisotropic displacement parameters for hydrogen atoms using an ONIOM approach, Acta Cryst. (2006) B62, 875-888.
Whitten, A.E., McKinnon, J.J., Spackman, M.A., Electric field-derived point charges to mimic the electrostatics in molecular crystals, J. Comput. Chem. (2006) 27, 1063-1070.
Dittrich, B., Strumpel, M., Schäfer, M., Spackman, M.A., Koritsanszky, T., Invarioms for improved absolute structure determination of light-atom crystal strcutures, Acta Cryst. (2006) A62, 217-223.
Whitten, A.E., Radford, C.J., McKinnon, J.J., Spackman, M.A., Dipole and quadrupole moments of molecules in crystals: A novel approach based on integration over Hirshfeld surfaces, J. Chem. Phys. (2006) 124, 074106.
Spackman, M.A., The use of the promolecular charge density to approximate the penetration contribution to intermolecular elextrostatic energies, Chem. Phys. Lett. (2006) 418, 158-162.
- Roles, responsibilities and expertise
- Prof. Spackman is currently Chair of the Discipline of Chemistry in the School of Biomedical, Biomolecular & Chemical Sciences
- Funding received
- ARC Discovery Grant and Australian Professorial Fellowship 2004-2008
ARC Discovery Grant 2008-2010, with Dr George Koutsantonis and Prof Bo lversen (Aarhus University, Denmark)
ARC Linkage International Grant 2008-2009, with A/Prof Dylan Jayatilaka and Prof Hans-Beat Bürgi (University of Bern, Switzerland)
ARC Discovery Grant 2009-2011
- Society of Crystallographers Australia and New Zealand (SCANZ)
- Honours and awards
- Finalist for the Australian Museum 2008 Eureka Prize for Scientific Research
- Prof Spackman currently co-supervises Alexandra Nemkevich (PhD) with Dr Ben Corry
- Current external positions
- Prof. Spackman is a Co-Editor of Acta Crystallographica Section B, and a member of the Editorial Board of CrystEngComm.
- Useful links
- CrystalExplorer is a fully-featured molecular crystal visualization tool, available for Mac OS X, Windows and Linux. CrystalExplorer provides a new way of visualizing molecular crystals using the full suite of Hirshfeld surface tools. (see http://ra.bcs.uwa.edu.au/CrystalExplorer/index.html)
The CrystalExplorer Wiki is located at http://ra.bcs.uwa.edu.au/CrystalExplorer/wiki/index.php/Main_Page
- Current projects
- ARC funding was 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 has developed and implemented innovative approaches in the charge density analysis of high-resolution, low-temperature single-crystal X-ray diffraction data, and obtained in-crystal estimates of the electronic part of molecular (hyper)polarisabilities and related bulk susceptibilities. This research exploited advances in CCD technology for X-ray data collection, procedures for electron density and wavefunction fitting, and analysis of molecular dynamics in crystals. Outcomes so far include insights into dipole moment enhancement due to hydrogen bonding and other crystal field effects [65, 69, 84, 85], investigation of approaches for estimating anisotropic displacement parameters for hydrogen atoms [68, 90], and polarizabilities and refractive indices obtained from wavefunction fitting to X-ray data [74, 92]. Results on hyperpolarizabilities and related susceptibilities are in preparation for publication.
ARC funding (2005-2008) has also supported recent work related to the development of computational tools based on Hirshfeld surfaces has focused on using the fingerprint plots to quantitatively compare crystal structures , treating disorder and polymorphism [79, 87], breaking down the surface and fingerprint plots , and mapping the ab initio electrostatic potential . Full details and up to date results from exciting work can be found on our web site.
More recent ARC funding support (2008-2010) underwrites a collaborative project with George Koutsantonis (UWA) and Bo Iversen (Aarhus, Denmark) studying intermolecular interactions and the properties of host-guest systems in the solid state, particularly organic clathrates and complexes formed by small molecules interacting with crown ethers, calixarenes, molecular tweezers and cages. This will be accomplished by exploiting the techniques of modern experimental charge density analysis using highly accurate X-ray diffraction data, complementary neutron diffraction experiments, quantum chemical calculations and computer graphics. A particular focus of the charge density analyses will be the polarization and dipole moment of guest molecules as a function of the changing electrostatic nature of the host systems.
Prof Spackman has links to research groups all over the world, including the US, Denmark, Switzerland, Italy and the United Kingdom. His collaborators within UWA are:
A/Prof Dylan Jayatilaka- development of novel computational tools for crystal engineering; nonlinear optical properties from experimental charge density studies
Dr Ben Corry- molecular dynamics studies of molecular crystals
Dr George Koutsantonis- experimental charge density studies of supramolecular host-guest complexes
- Research profile
Research profile and publications