John B. Parise
B.Sc., James Cook University, 1977
Professor Parise is a mineralogist and solid state chemist interested in Earth materials materials synthesis and the determination of atomic arrangements in condensed matter. The Parise group maintains an eclectic mix of projects, tied together by one guiding principle: We care about where the atoms are, and where they end up after changes in environmental conditions. No matter what the particular composition of the condensed matter its functionality is dependent on where the atoms are and where they end up after they respond to changes in P, T, Eh, pH, etc) - think graphite - diamond, Ice - water, DNA to remind yourselves of the fundamental need to determine where the atoms are under the operating conditions of interest. With that appreciation, the tools developed to study the mineralogy and reactivity in extreme Earth environments are often applicable to technologically interesting materials and materials in extra-terrestrial environments
In order to determine atomic level information under a material's "operating conditions" the group collaborates with researchers nationally and internationally at X-ray synchrotron and neutron sources and has developed a number of environmental cells for work at these facilities. Stony Brook is only 20 minutes from the Brookhaven National Laboratory (BNL) where much of this work is carried out. Among the techniques utilized at Stony Brook and BNL are single-crystal and powder X-ray, neutron and electron diffraction, and X-ray absorption (EXAFS and XANES).
The group places a strong emphasis on synthesis and students make the samples they later characterize. With the development of state-of-the-art diffraction facilities and high-pressure, high-temperature synthetic apparatus at Stony Brook and Brookhaven National Laboratory, unique opportunities exist for Stony Brook scientists to become involved in synthesis and characterization experiments.
The structure of nano-crystalline minerals
Structural studies based on the interpretation of Bragg diffraction, in situ and time resolved, at ambient and non-ambient conditions, is the mainstay of our ability to understand, predict and modify the physical and chemical properties of materials, including minerals. Over 20 noble prizes related to "Bragg crystallography" are testimony to the enduring power and importance of a technique that unambiguously tells us "where the atoms are". There are important materials where considerable structural disorder impedes the Bragg scattering approach however. Derivation of testable structural models for these materials has lagged because of a lack of suitable X-ray and neutron radiation sources to provide the counting statistics sufficient to measure elastic coherent diffuse scattering in the presence of dominant inelastic background and Bragg scattering. For proper normalization these data need to be measured to high Q to provide quantitative pair distribution functions (PDF) to compare to theoretical models. These PDFs also have to be of sufficient resolution to observe subtle deviations that might be crucial to distinguishing closely related structure models. With the increasing availability of high energy beams, particularly with focusing above 100 keV, and spallation source neutrons increasingly better quality PDFs are becoming available. This is already impacting studies of glasses, melts and nano-crystalline materials. Other "extreme conditions" such as kinetic studies of nano-crystalline materials growth in proteins may also be possible.
Ferrihydrite structure revealed:
Ferrihydrite, an iron oxide typically described by the composition Fe5HO8•4H2O, is a naturally occurring material that is widely found at or near the Earth’s surface, and is implicated as a possible phase on the martian surface. Ferrihydrite could also have significant industrial applications because it can adsorb chemical species detrimental to the environment, including those containing heavy metals and arsenic.
Despite its ubiquity in nature, possible use in environmental remediation, and being the subject of well over 100 technical papers per year, ferrihydrite is something of a mystery. It occurs only as a nanoparticle, and although it is technically classified as a mineral – substances that are natural and homogeneous with a clearly defined chemical composition – there has been a lack of consensus regarding ferrihydrite’s crystal structure, homogeneity, and even basic composition.
The structure of ferrihydrite has been difficult to discover because it is "x-ray amorphous," meaning that typical laboratory-based x-ray diffraction instrumentation are not specific enough to resolve its structure. Graduate student Marc Michel working with ABRC professors Daniel Strongin, Martin Schoonen, John Parise, and other collaborators, recently solved the mystery surrounding the structure of ferrihydrite using total X-ray scattering experiments and then analyzing the data using the atomic pair distribution, or PDF, method.
The reliability and information-rich nature of the PDF method requires a high-energy x-ray beam, available at third-generation synchrotron x-ray sources. The PDF created with this high-energy x-ray is a real-space representation of the distances between all pairs of atoms in the structure. This data can then be used to test models of nanoparticle structure.
To obtain the structure of ferrihydrite several possible structural models were created, and then the PDFs generated from them were compared to the experimentally derived PDF of ferrihydrite. The structural model that best fit the experimental data consisted of both tetrahedral and octahedrally coordinated iron arranged in a structural motif that was closely related to the Baker-Figgis δ-Keggin cluster. Not only did this analysis reveal a structural model that best fit the experimental data, it also showed that other recently proposed structural models of ferrihydrite did not match the data very accurately at all. This is very convincing evidence that the ABRC team from Stony Brook and Temple have actually resolved the structure of the once mysterious mineral. With this model now in hand, the functionality of ferrihydrite, and those hundreds of technical papers, can be explored from a firm structural basis.
High pressure studies
We are interested in issues such as the pressure stability, structure and ordering in hydrogen bonded systems and oxides displaying order-disorder transitions, and in determining if these might affect seismicity. We study materials in situ using diamond anvil techniques and large volume high pressure apparatus at the BNL, Grenoble (France) and at the Rutherford Lab. (UK) and other national and international facilities. These materials often accommodate changes in composition, temperature, and pressure through displacive phase transitions. No bond breaking is involved and the changes can be followed in situ using conventional X-ray and neutron diffraction techniques. When the changes are reconstructive, involving bond breaking and bond making, the intermediate stages, important in determining the mechanisms for such transitions, can be studied using the techniques of X-ray absorption and scattering.
Studies of these phase transitions are important for determining the factors responsible for structural stability and changes in sound velocity, which are studied in collaboration with the groups of Professors Liebermann and Li. This knowledge enhances our ability to predict these changes under particular environmental conditions inside the earth.
Post-perovskite: Understanding observations of seismic anisotropy and ultra-low velocity zones at the bottom of Earth's mantle requires knowledge of the Clapeyron slope of the perovskite/post-perovskite phase transition in MgSiO3, the dominant mineral in the lower mantle (see Garnero web site http://garnero.asu.edu/research_images/index.html). While large uncertainties associated with experimental apparatus prohibit characterization of the Clapeyron slope in situ structure data suggest that this parameter describing the pressure-temperature relationship of phase transition between perovskite and post-perovskite structure can be estimated based on crystal structure and extrapolation of the volume-ratio between the two cation-centered polyhedra - a parameter sensitive to tilting of the corner-sharing octahedra characteristic of the perovskite structure framework. Post-perovskite adopts the CaIrO3 structure model and we are systematically studying the rheology, elasticity, texture and crystal structure of this material as an analogue to MgSiO3. Many results from previous studies, because of the very high pressures involved, suffer from preferred orientation. Graduate student Dave Martin has solved this problem and improved the fit of structure models to the diffraction data, by developing and implementing a gasket insert for the diamond anvil cell.
Engineering Novel Frameworks
Zeolites and synthetic molecular sieves are useful materials for separations technologies. We are interested in not only how natural systems exchange, sequester and release ions, but also in how to apply the knowledge derived from basic science studies of natural systems to synthetic materials as well. A recent case in point is the application of methodologies for micro-crystalline diffraction developed at the National Synchrotron Light Source (NSLS) and the Advanced Photon Source (APS) to determination of structure for important ion exchangers such as those studied jointly with the Sandia National Laboratory and RUB, Germany. Lithosilicate materials developed in collaboration with our German colleagues also hold promise as ion conductors and for gas-separation.
The functionality of these as well as naturally occurring materials such as aluminosilicate zeolites, need to be understood in the context of their atomic structures. More recently we have synthesized novel metal organic frameworks and are exploring the hydrogen sorption capacity of these materials. Here are a couple of pretty pictures of beautiful structure determined either in our lab or at synchrotron X-ray facilities (NB the compound left was synthesized and solved by graduate student Hyunsoo Park; the one right was synthesized in the lab of Professor Hongcai Joe Zhou at Miami of Ohio http://www.cas.muohio.edu/nanotech/faculty/Dr_Hongcai_Zhou.html and solved by postdoc Paul Forster.
Time resolved studies
Understanding the underlying atomistic mechanisms responsible for a material's functionality is considered a prerequisite for establishing methodologies that control its properties. Subtle structural variation in proteins giving rise to dramatic changes in functionality is well-known.
Combining information from time-resolved X-ray and neutron scattering with theoretical calculations, reveals the dynamics and subtle interplay between framework, exchangeable cations and water in CST, a structure much-studied because of its remarkable selectivity toward certain radionuclides. Rather than a simple ion displacement reaction, selective exchange is mediated through repulsive interactions between water and an intermediate cesium site in the channels, which in turn repels a hydrogen "lever ". These repulsive interactions induce a conformational rearrangement that unlocks the preferred Cs-site and increases the capacity.
Lee, Y., Vogt, T., Hriljac, J. A., Parise, J. B., Hanson, J., and Kim, S.-J (2002) Non-framework cation migration and irreversible pressure-induced hydration in a zeolite, Nature, 420, 485- 489
Lee, Y., Martin C. D., Parise, J. B., Hriljac, J. A., and Vogt T. (2004) Formation and manipulation of confined water wires, Nano Letters 4, 619-621
Martin, C. D., Antao, S. M., Chupas, P. J., Lee, P. L., Shastri, S. D. and Parise, J. B. (2005) Quantitative High Pressure Pair Distribution Function Analysis of Nanocrystalline Gold, Appl. Phys. Lett. 86, 061910-1 - 061910-3
Parise, J. B., Antao, S. M., Martin, C. D. and Crichton, W. (2005) Diffraction studies of order-disorder at high pressures and temperatures Powder Diffraction 20, 80-86
McIntyre, G. J., Melesi, L., Guthrie, M., Tulk, C. A., Xu, J. and Parise, J. B. (2005) One picture says it all—high-pressure cells for neutron Laue diffraction on VIVALDI J. Phys.: Condens. Matter 17, S3017–S3024 doi:10.1088/0953-8984/17/40/004
Parise, J. B., Antao, S. M., Michel, F. M., Martin, C. D., Chupas, P. J. and Lee, P. L. (2005) Quantitative high-pressure pair distribution function analysis, J. Synchrotron Rad. 12, 554-559
Park, S.-H., Boysen, H. and Parise, J. B. (2006) Structural disorder of a new zeolite-like lithosilicate, K2.6Li5.4[Li4Si16O38 ]•4.3H2O Acta Crystallog Section B 62, 42-51
Lee, Y., Hriljac, J. A., Parise, J. B., Vogt, T. (2006) Pressure-Induced hydration in zeolite tetranatrolite Am. Mineral. 91, 247-251
Parise J. B., Brown G. E. (2006) New opportunities at emerging facilities, ELEMENTS 2, 37-42
Martin, C. D., W. A. Crichton, H. Liu, V. Prakapenka, J. Chen, and J. B. Parise (2006), Phase transitions and compressibility of NaMgF3 (Neighborite) in perovskite- and post-perovskite-related structures, Geophys. Res. Lett., 33, L11305, doi:10.1029/2006GL026150
Mei, Q., C. J. Benmore, R. T. Hart, E. Bychkov, P. S. Salmon, C. D. Martin, F. M. Michel, S. M. Antao, P. J. Chupas, P. L. Lee, S. D. Shastri, J. B. Parise, K. Leinenweber, S. Amin, and J. L. Yarger (2006) Topological changes in glassy GeSe2 at pressures up to 9.3 GPa determined by high-energy x-ray, and neutron diffraction measurements Phys. Rev. B74 014203
Parise, J. B., Locke, D. R., Tulk, C. A., Swainson, I. and Cranswick, L. (2006) The effect of pressure on the Morin transition in hematite (α-Fe2O3) Physica B, 385-386, 391-393
Parise, J. B. (2006) ) Introduction to Neutron Properties and Applications in Neutron Studies in Earth Sciences H-R. Wenk, Ed. Reviews in Mineralogy and Geochemistry series editor JJ Rosso (Ed) Vol 63, pp 1 - 27
Parise, J. B. (2006) High Pressure Studies in Neutron Studies in Earth Sciences H-R. Wenk, Ed. Reviews in Mineralogy and Geochemistry series editor JJ Rosso (Ed) Vol 63, pp 205-233
Forster, P. M.; Eckert, J.; Heiken, B. D.; Parise, J. B.; Yoon, J. W.; Jhung, S. H.; Chang, J.-S.; Cheetham, A. K. (2006) Adsorption of Molecular Hydrogen on Coordinatively Unsaturated Ni(II) Sites in a Nanoporous Hybrid Material, J. Am. Chem. Soc. 128, 16846-16850
Michel, F. M., Ehm, L., Liu, G., Han, W. Q., Antao, S. M., Chupas, P. J., Lee, P. L., Knorr, K., Eulert, H., Kim, J., Grey, C. P. , Celestian, A. J., Gillow, J., Schoonen, M. A. A., Strongin, D. R. and Parise, J. B. (2007) Similarities in 2- and 6-Line Ferrihydrite Based on Pair Distribution Function Analysis of X-ray Total Scattering, Chem. Materials, 19, 1489-1496
Celestian, A. J., Parise, J. B., Smith, R. I., Toby, B., H. and Clearfield, A. (2007) Role of the hydroxyl-water hydrogen-bond network in structural transitions and selectivity toward cesium in Cs0.38(D1.08H0.54)SiTi2O7·(D0.86 H0.14)2O crystalline silicotitanate Inorg. Chem. 46, 1081-1089
Park, H., Britten, J. F., Mueller, U., Lee, J-Y., Li, J. and Parise, J. B. (2007) Synthesis, structure determination, and hydrogen sorption studies of new metal-organic frameworks using triazole and naphthalenedicarboxylic acid, Chem. Mater. 19, 1302-1308
Michel, F. M., Ehm, L., Antao, S. M., Chupas, P. J., Lee, P., Liu, G., Strongin, Schoonen, M. A. A., Phillips, B. L. and Parise, J. B. (2007) The structure of ferrihydrite, a nanocrystalline material, Science, 316, 1726-1729
Martin, C. D., Chupas, P. J., Chapman, K. W. and Parise, J. B. (2007) Compression, thermal expansion, structure, and instability of CaIrO3, the structure model of MgSiO3 post-perovskite, Am Mineral. 92, 1048-1053
News & Announcements
Geosciences Department Newsletter
Professor Timothy Glotch to lead NASA funded research team
Professor Martin Schoonen named Chairman of the Environmental Sciences Department at BNL
Professors John Parise and Artem Oganov pursue Materials Genome Initiative
Professor Deanne Rogers finds evidence for past groundwater on Mars
Professor Robert Liebermann accepts Edward A. Flinn Award
Professor Scott McLennan selected for NASA's Mars Science Laboratory Team