Spackman, Mark - University of Western Australia - School of Chemistry and Biochemistry

研究领域

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.

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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 calix[4]arene, 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, 19‐32. 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.