Organisers

• Martijn A. Zwijnenburg (Departament de Química Física, Universitat de Barcelona)
• Scott Woodley (DFRL, Department of Chemistry, University College London)

Supports

 CECAM

Description

To predict which distinct polymorphs of a material (e.g. SiO2 or ZnO) are likely to be formed during synthesis is, one might argue, the holy grail of computational solid state chemistry. This would not only allow one to rationalise synthesis routes towards a particular polymorph and highlight promising areas of the periodic table for experimental exploration but also provide insight as to whether a certain desired property (e.g. a large pore-size in the case of nanoporous zeolites) is obtainable for a given chemical composition. In practice this is a challenging problem as besides thermodynamics it requires an accurate calculation of nucleation and growth kinetics - something that is in principle possible, but currently computationally intractable for all but the simplest systems due to the inherent complexity and/or long simulations times required. However, even when one ignores kinetic issues it is still possible to make very relevant predictions about the fate of polymorphs during synthesis. Through a careful calculation of a material’s (free) energy landscape one can derive the material’s phase diagram, showing which polymorphs are thermodynamically stable for a given pressure and temperature. Moreover, one can then characterise metastable polymorphs in terms of their (free) energy difference with the stable polymorph and the number of other metastable polymorphs close lying in (free) energy. Finally, one can prepare databases of such hypothetical (metastable) polymorphs for a given chemical composition. To date such studies have been mostly limited to simple alkali salts and silica (including siliceous zeolites) but potentially this methodology can be applied to materials formed from the complete periodic table. Proof of the latter is the very recent theoretical work into polymorphism of such systems as AlF3, SiS2 and ZnO.

Scientific Objectives

By bringing together experts in the diverse fields of global optimisation, enumeration of crystal structures, interatomic potentials, periodic density functional theory, thermochemistry and experimental materials chemistry we hope to gain insight into open questions, such as:

(I) What is the best way to find low energy structures and the global minimum for periodic solids (using simulated annealing, genetic algorithms or structural analogies)?

(II) What is the best way to convert a hypothetical topology into the atom coordinates of a real material?

(III) What accuracy is required from our models and how do we check them in the absence of experimental thermochemical data?

(IV) Is massive polymorphism unique to tetrahedral materials like silica and ice?

(V) Does knowing the energy landscape for a given chemical composition help experimentalists to plan a synthesis route towards a hypothetical material?

(VI) Is it worth the effort of calculating a phase diagram and/or a global minimum when experimentalists can synthesize metastable phases?

(VII) Can the predicted properties for hypothetical materials help in the experimental characterisation of new synthetic products and/or in the design of new chemical processes?

Besides this, we aim with this meeting to stimulate the exchange of ideas between the various fields and between theory and experiment. One way through which we will try to achieve this goal is by inviting three keynote speakers to set the scene by providing an overview of the state of the art in respectively structure enumeration, global optimisation and synthesis planning. Another way will be by asking all speakers at the workshop to answer at least one of the questions above in their contribution.

References

[1] M.A. Zwijnenburg, F. Cora, R.G. Bell Dramatic Differences between the Energy Landscapes of SiO2 and SiS2 Zeotype Materials., JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 129 12588 (2007)

[2] S.T. Bromley A computational study into the viability of new molecular materials polymorphs based on fully-coordinated inorganic nanoclusters., CRYSTENGCOMM 9 463 (2007)

[3] M.H.F. Sluiter Lattice stability prediction of elemental tetrahedrally close-packed structures., ACTA MATERIALIA 55 3707 (2007)

[4] M.A. Zwijnenburg, F. Cora, R.G. Bell On the performance of DFT and interatomic potentials in predicting the energetics of (three-membered ring-containing) siliceous materials., JOURNAL OF PHYSICAL CHEMISTRY B 111 6156 (2007)

[5] J.C. Schoen, I.V. Pentin, M. Jansen Ab initio computation of the low-temperature phase diagrams of the alkali metal iodide-bromides., JOURNAL OF PHYSICAL CHEMISTRY B 111 3943 (2007)

[6] S.M. Woodley Engineering microporous architectures: combining evolutionary algorithms with predefined exclusion zones., PHYSICAL CHEMISTRY CHEMICAL PHYSICS 9 1070 (2007)

[7] G. Thimm, B. Winkler Net topologies, space groups, and crystal phases., ZEITSCHRIFT FUR KRISTALLOGRAPHIE 221 749 (2006)

[8] G.A. Tribello, B. Slater, C.G. Salzmann A blind structure prediction of ice XIV., JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 128 12594 (2006)

[9] A. Le Bail, F. Calvayrac Hypothetical AlF3 crystal structures., JOURNAL OF SOLID STATE CHEMISTRY 179 3159 (2006)

[10] A.W.C. van den Berg, M.A. Zwijnenburg, S.T. Bromley, E. Flikkema, R.G. Bell, J.C. Jansen, J. Schoonman Comparing the influence of framework type on H-2 absorption in hypothetical and existing clathrasils: a grand canonical Monte Carlo study., JOURNAL OF MATERIALS CHEMISTRY 16 3285 (2006)

[11] S.A. Wells, M.D. Foster, M.M.J. Treacy A simple geometric structure optimizer for accelerated detection of infeasible zeolite graphs., MICROPOROUS AND MESOPOROUS MATERIALS 93 151 (2006)

[12] D.J. Earl, M.W. Deem Toward a database of hypothetical zeolite structures., INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH 45 5449 (2006)

[13] Z. Cancarevic, J.C. Schoen, M. Jansen Stability of alkali-metal oxides as a function of pressure: Theoretical calculations., PHYSICAL REVIEW B 73 224114 (2006)

[14] C. Mellot-Draznieks, G. Ferey Assembling molecular species into 3D frameworks: Computational design and structure solution of hybrid materials., PROGRESS IN SOLID STATE CHEMISTRY 33 187 (2005)

[15] M.Jansen, J.C. Schoen "Design" in chemical synthesis - An illusion?, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 45 3406 (2006)

[16] J. Dutour, G. Ferey, C. Mellot-Draznieks Structures and energetics of open-framework germanates; Exploration of hypothetical zeolitic GeO2 structures based on D4R units., SOLID STATE SCIENCES 8 241 (2006)

[17] J.C. Wojdel, M.A. Zwijnenburg, S.T. Bromley Magic silica clusters as nanoscale building units for super-(tris)tetrahedral materials., CHEMISTRY OF MATERIALS 18 1464 (2006)

[18] M.D. Foster, M.M.J. Treacy, J.B. Higgins, I. Rivin, E. Balkovsky, K.H. Randall A systematic topological search for the framework of ZSM-10., JOURNAL OF APPLIED CRYSTALLOGRAPHY 38 1028 (2005)

[19] A. Simperler, M.D. Foster, O.D. Friedrichs, R.G. Bell, F.A.A. Paz, FAA, J. Klinowski Hypothetical binodal zeolitic frameworks., ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE 61 263 (2005)

[20] Z. Cancarevic, J.C. Schoen, M. Jansen Prediction of possible high-pressure phases of Cu3N., ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE 631 1167 (2005)

[21] H. Kabbour, L. Cario, F. Boucher Rational design of new inorganic compounds with the ZrSiCuAs structure type using 2D building blocks., JOURNAL OF MATERIALS CHEMISTRY 15 3525 (2005)

[22] A. Le Bail Inorganic structure prediction with GRINSP., JOURNAL OF APPLIED CRYSTALLOGRAPHY 38 389 (2005)

[23] L. Cario, H. Kabbour, A. Meerschaut Designing new inorganic compounds from 2D building blocks., CHEMISTRY OF MATERIALS 17 234 (2005)

[24] C. Mellot-Draznieks, J. Dutour, G.R. Ferey Hybrid organic-inorganic frameworks: Routes for computational design and structure prediction., ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 43 6290 (2004)

[25] J.C. Schoen Enthalpy landscapes of the earth alkaline metal oxides., ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE 630 2354 (2004)

[26] M.M.J. Treacy, I. Rivin, E. Balkovsky, K.H. Randall, M.D. Foster Enumeration of periodic tetrahedral frameworks. II. Polynodal graphs., MICROPOROUS AND MESOPOROUS MATERIALS 74 121 (2004)

[27] R.T. Strong, C.J. Pickard, V. Milman, G. Thimm, B. Winkler Systematic prediction of crystal structures: An application to sp(3)-hybridized carbon polymorphs., PHYSICAL REVIEW B 70 045101 (2004)

[28] J.C. Schoen, Z. Cancarevic, M. Jansen Structure prediction of high-pressure phases for alkali metal sulfides., JOURNAL OF CHEMICAL PHYSICS 121 2289 (2004)

[29] S.M. Woodley, P.D. Battle, J.D. Gale, C.R.A. Catlow Prediction of inorganic crystal framework structures - Part 1: Using a genetic algorithm and an indirect approach to exclusion zones., PHYSICAL CHEMISTRY CHEMICAL PHYSICS 6 1815 (2004)

[30] S.M. Woodley Prediction of inorganic crystal framework structures - Part 2 - Using a genetic algorithm and a direct approach to exclusion zones., PHYSICAL CHEMISTRY CHEMICAL PHYSICS 6 1823 (2004)

[31] M.D. Foster, A. Simperler, R.G. Bell, O.D. Friedrichs, F.A.A. Paz, J. Klinowski Chemically feasible hypothetical crystalline networks., NATURE MATERIALS 3 234 (2004)

[32] D. Fischer, Z. Cancarevic, J.C. Schoen, M. Jansen Synthesis and structure of K3N., ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE 630 156 (2004)

[33] A. Simperler, M.D. Foster, R.G. Bell, J. Klinowski Hypothetical uninodal zeolite structures: Comparison of AlPO4 and SiO2 compositions using computer simulation., JOURNAL OF PHYSICAL CHEMISTRY B 108 869 (2004)

[34] S.M. Woodley, C.R.A. Catlow, P.D. Battle, J.D. Gale The prediction of inorganic crystal framework structures using excluded regions within a genetic algorithm approach., CHEMICAL COMMUNICATIONS 22 (2004)

[35] J.C. Schoen, M.A.C. Wevers, M. Jansen 'Entropically' stabilized region on the energy landscape of an ionic solid., JOURNAL OF PHYSICS-CONDENSED MATTER 15 5479 (2003)

[36] M.D. Foster, O.D. Friedrichs, R.G. Bell, F.A.A. Paz, J. Klinowski Structural evaluation of systematically enumerated hypothetical uninodal zeolites., ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 42 3896 (2003)

[37] C. Mellot-Draznieks, S. Girard, G. Ferey Novel inorganic frameworks constructed from double-four-ring (D4R) units: Computational design, structures, and lattice energies of silicate, aluminophosphate, and gallophosphate candidates., JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 124 15326 (2002)

[38] C. Mellot-Draznieks, S. Girard, G. Ferey, J.C. Schoen, Z. Cancarevic, M. Jansen Computational design and prediction of interesting not-yet-synthesized structures of inorganic materials by using building unit concepts., CHEMISTRY-A EUROPEAN JOURNAL 8 4103 (2002)

[39] J.C. Schoen, M. Jansen Determination, prediction, and understanding of structures, using the energy landscapes of chemical systems - Part III., ZEITSCHRIFT FUR KRISTALLOGRAPHIE 216 361 (2001)

[40] J.C. Schoen, M. Jansen Determination, prediction, and understanding of structures, using the energy landscapes of chemical systems - Part I., ZEITSCHRIFT FUR KRISTALLOGRAPHIE 216 307 (2001)

[41] M.A.C Wevers, J.C. Schoen, M. Jansen Characteristic regions on the energy landscape of MgF2., JOURNAL OF PHYSICS A-MATHEMATICAL AND GENERAL 34 4041 (2001)

[42] B. Winkler, C.J. Pickard, V. Milman, G. Thimm. Systematic prediction of crystal structures, CHEMICAL PHYSICS LETTERS 337 36 (2001)

[43] J.C. Schoen, M.A.C. Wevers, M. Jansen Prediction of high pressure phases in the systems Li3N, Na3N,(Li,Na)(3)N, Li2S and Na2S., JOURNAL OF MATERIALS CHEMISTRY 11 69 (2001)

[44] B. Winkler, C.J. Pickard, V. Milman, W.E. Klee, G. Thimm Prediction of a nanoporous sp(2)-carbon framework structure by combining graph theory with quantum mechanics., CHEMICAL PHYSICS LETTERS 312 536 (1999)

[45] M.A.C. Wevers, J.C. Schoen, M. Jansen Global aspects of the energy landscape of metastable crystal structures in ionic compounds., JOURNAL OF PHYSICS-CONDENSED MATTER 11 6487 (1999)

[46] S.M. Woodley, P.D. Battle, J.D. Gale, C.R.A. Catlow The prediction of inorganic crystal structures using a genetic algorithm and energy minimisation., PHYSICAL CHEMISTRY CHEMICAL PHYSICS 1 2535 (1999)

[47] F. Cora, D.W. Lewis, C.R.A. Catlow De novo design of microporous transition metal oxides., CHEMICAL COMMUNICATIONS 1943 (1998)

[48] M.A.C Wevers, J.C. Schoen, M. Jansen Determination of structure candidates of simple crystalline AB(2) systems., JOURNAL OF SOLID STATE CHEMISTRY 136 233 (1998)

[49] M. Jansen, J.C. Schoen Structure candidates for the alkali metal nitrides., ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE 624 533 (1998)

[50] M.M.J. Treacy, K.H. Randall, S. Rao, J.A. Perry, D.J. Chadi Enumeration of periodic tetrahedral frameworks., ZEITSCHRIFT FUR KRISTALLOGRAPHIE 212 768 (1997)