Anorganische Kristallchemie Zeitplan 1.-4. Woche Ionenkristalle Perowskit kovalente anorganische Verbindungen Zeolithe DLS (Geometrie optimierung) intermetallische Verbindungen 5.-6. Woche Pulverdiffraktometrie 7. Woche Quasikristalle W. Steurer 7.-15. Woche organische Kristallchemie und B. Schweizer Strukturdatenbanken

Kristallchemie und Kristallstrukturdatenbanken Pulverdiffraktometrie Einkristall Strukturanalyse Strukturanalyse mittels Pulverdaten Kristallchemie in der Strukturanalyse Modellbau Simulated annealing Evolutionäre Algorithmen FOCUS Charge flipping

FOCUS Zeolithe 3-dimensionale, 4-fach verknüpfte Gerüststruktur

FOCUS Zeolithe 3-dimensionale, 4-fach verknüpfte Gerüststruktur Eckenverknüpfte TO4 Tetraeder

FOCUS Zeolithe 3-dimensionale, 4-fach verknüpfte Gerüststruktur Eckenverknüpfte TO4 Tetraeder bekannte T-O Bindungslängen, O-T-O und T-O-T Winkel O-Si-O 109.5˚ Si-O-Si 145˚ Si-O 1.61 Å

FOCUS approximate unit cell contents individual minimum distances selected reflection intensities FOCUS starting phases electron density map peak search assignment of atoms by peak height minimum distances assignment of atoms to largest fragment framework search framework classification histogram new phase set convergence? no yes

FOCUS AlPO-ZON a 14.548 Å b 15.301 Å c 16.629 Å Raumgruppe Pbca approximate unit cell contents individual minimum distances selected reflection intensities FOCUS AlPO-ZON a 14.548 Å b 15.301 Å c 16.629 Å Raumgruppe Pbca Chemische Zusammensetzung |(RF)x|[Al32P32O128] V = 3956 Å3 16 T-Atome pro 1000 Å3 3.1 Å Al - Al Al - P P - P Al - O P - O 2.6 Å 1.4 Å 1.6 Å O - O 2.3 Å 2.7 Å

AlPO-ZON a = 14.548 Å, b = 15.301 Å, c = 16.629 Å Pbca 10 15 20 25 30 35 40 45 AlPO-ZON a = 14.548 Å, b = 15.301 Å, c = 16.629 Å Pbca

FOCUS approximate unit cell contents individual minimum distances selected reflection intensities FOCUS starting phases electron density map peak search assignment of atoms by peak height minimum distances assignment of atoms to largest fragment framework search framework classification histogram new phase set convergence? no yes

Peak-Positionen und -Höhen

FOCUS approximate unit cell contents individual minimum distances selected reflection intensities FOCUS starting phases electron density map peak search assignment of atoms by peak height minimum distances assignment of atoms to largest fragment framework search framework classification histogram new phase set convergence? no yes

Atome durch Peakhöhe und miminale Abstände zugeordnet

FOCUS approximate unit cell contents individual minimum distances selected reflection intensities FOCUS starting phases electron density map peak search assignment of atoms by peak height minimum distances assignment of atoms to largest fragment framework search framework classification histogram new phase set convergence? no yes

Atome durch grösstes Fragment zugeordnet

Atome durch grösstes Fragment zugeordnet

assignment of atoms to largest fragment assignment of atoms by peak height minimum distances assignment of atoms to largest fragment new phase set Elektronendichte Strukturfaktor Streufaktor berechnete Phasen gemessene Amplituden

FOCUS approximate unit cell contents individual minimum distances selected reflection intensities FOCUS starting phases electron density map peak search assignment of atoms by peak height minimum distances assignment of atoms to largest fragment framework search framework classification histogram new phase set convergence? no yes

Gerüst-Klassifikation Wie kann man ein Gerüst eindeutig erkennen? Coordination sequence 4 9 16 25 37 53 73 96 120 145 Loop configuration Vertex symbol 4 · 4 · 4 · 6 · 6 · 12

VPI-9 Chemische Zusammensetzung Original K4Rb20[Si48Zn12O120]·64H2O NH4-ausgetauscht (NH4)24[Si48Zn12O120]·64H2O Daten Original NH4-ausgetauscht Synchrotron SNBL an ESRF SNBL an ESRF Wellenlänge 0.99995 Å 0.94734 Å Elementarzelle Raumgruppe P41212 P42/ncm a 9.8837 Å 9.8946 Å c 73.6505 Å 36.8715 Å P41212 73.6505 Å

VPI-9 - FOCUS Input Raumgruppe P42/ncm Elementarzelle a 9.8946 Å b 36.8715 Å Atome / EZ Zn (4-fach verknüpft) 12 12 Si (4-fach verknüpft) 44 48 O (brückend) 112 120 minimale Abstände Zn - O 1.7 Å Zn - Si 2.9 Å Si - O 1.5 Å Zn - Zn 4.0 Å O - O 2.3 Å Si - Si 2.9 Å Reflexe 258 Gerüst-Typen gefunden (übernacht) 1356 (ein Typ 102 Mal gefunden)

Histogramm der Gerüst-Typen wahrscheinlichster Gerüst-Typ Gerüst-Typen

Gerüststruktur mit 7 (Si,Zn) pro asymmetrische Einheit VPI-9 Gerüststruktur mit 7 (Si,Zn) pro asymmetrische Einheit

VPI-9 Rubidium Zinkosilikat VPI-9 12 Si, 3 Zn, 30 O, 9 Rb, 2 K und 3 H2O pro asymmetrische Einheit

Kristallchemie und Kristallstrukturdatenbanken Pulverdiffraktometrie Einkristall Strukturanalyse Strukturanalyse mittels Pulverdaten Kristallchemie in der Strukturanalyse Modellbau Simulated annealing Evolutionäre Algorithmen FOCUS Charge flipping

Charge Flipping |Fhkl(obs)| δ (ed threshold for flipping) phase shifts for weak reflections? assign random phases electron density map flip sign of ed < δ alternative method of ab initio structure determination for single crystals introduced by Oszlanyi and Suto in 2004 algorithm - simple flow diagram, deceptively simple idea combine |Fhkl(obs)| with φhkl(calc) perturbed electron density map Fourier transform R-value (|Fhkl(calc)| vs |Fhkl(obs)| |Fhkl(calc)| φhkl(calc) Oszlányi, G. and Sütõ, A. (2004). Acta Cryst. A60, 134-141 Oszlányi, G. and Sütõ, A. (2005). Acta Cryst. A61, 1347-1352

Charge Flipping (powder) |Fhkl(obs)| with overlap groups δ (ed threshold for flipping) phase shifts for weak reflections? repartitioning after n cycles electron density histogram |Fhkl(obs)| δ (ed threshold for flipping) phase shifts for weak reflections? assign random phases new|Fhkl(obs)| electron density map flip sign of ed < δ repartition overlapping reflections superflip (powder?) features of charge flipping with powders using CF to repartition, begging the question noticed during testing that correct solution could be seen in the ed histogram use histogram matching to modify the ed map for repartitioning? learn more at Christian's poster combine |Fhkl(obs)| with φhkl(calc) perturbed electron density map |Fhkl(calc)| φhkl(calc) Fourier transform |Fhkl(calc)| φhkl(calc) R-value Fourier transform modified electron density map yes n cycles? no histogram matching

Histogram matching 12 Å 8 Å Electronendichte alle ¼ Å 48 x 32 x 20 5 Å Electronendichte alle ¼ Å 48 x 32 x 20 = 30720 points

Histogram matching Elektronendichte Werte nach Intensität ordnen Liste in 50 Bereiche aufteilen Durchschnittsdichte pro Bereich rechnen superflip (powder?) features of charge flipping with powders using CF to repartition, begging the question noticed during testing that correct solution could be seen in the ed histogram use histogram matching to modify the ed map for repartitioning? learn more at Christian's poster typischer Zeolith Karte nach ein paar Zyklen Charge Flipping

Powder Charge Flipping [Zr12P16O60(OH)4F8]

Powder Charge Flipping [Zr12P16O60(OH)4F8]