Die Präsentation wird geladen. Bitte warten

Die Präsentation wird geladen. Bitte warten

Kristallchemie und Kristallstrukturdatenbanken Pulverdiffraktometrie Einkristall Strukturanalyse Strukturanalyse mittels Pulverdaten Kristallchemie in.

Ähnliche Präsentationen


Präsentation zum Thema: "Kristallchemie und Kristallstrukturdatenbanken Pulverdiffraktometrie Einkristall Strukturanalyse Strukturanalyse mittels Pulverdaten Kristallchemie in."—  Präsentation transkript:

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

2 Simulated annealing und Zeolithe M.W. Deem and J.M. Newsam, "Determination of 4- connected framework crystal structures by simulated annealing" Nature 342, (1989) M. Falcioni and M.W. Deem, "A biased Monte Carlo scheme for zeolite structure solution" J. Chem. Phys. 110, (1999)

3 Simulated annealing und Zeolithe TT T T T T T TTT T T T T T TTT T T T T T TTT T T T T T T T T T T T T T TTT T T T T T T T T T T T T T T T T T T T T T T

4 T T T T T T T TTT T T T T T T T T T T T T T T T T T T T T T T T-T Abstände T-T-T Winkel Anzahl nächste Nachbaren Pulverdiagramm figure of merit figure of merit ( 2 ) ( 2 ) zufällige Verschiebung aller Atome

5 oder oder n < e - n < e - = ( 2 neu - 2 alt )/T = ( 2 neu - 2 alt )/T 2 neu < 2 alt 2 neu < 2 alt "Move" akzeptiert wenn T T T T T T T TTT T T T T T T T T T T T T T T T T T T T T T T Simulated annealing und Zeolithe T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T 2 neu - 2 alt klein und/oder T gross 2 neu - 2 alt klein und/oder T gross klein klein e - gross e - gross "Move" eher akzeptiert "Move" eher akzeptiert

6 T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T TTT T T T T T Simulated annealing und Zeolithe

7

8 chemische Zusammensetzung Verknüpfung Molekülstrukturen C 10 H 16 N 6 S Simulated annealing und Molekülstrukturen Cimetidine Bindungslängen, Bindungswinkel, Torsionswinkel

9 C - S1.82 ÅC - C - S109.5˚C - C - C - S180˚ N C - S1.82 ÅC - C - S109.5˚ Cimetidine Molekül kann mittels interne Koordinaten beschrieben werden HNHNHNHN N S HNHNHNHN HNHNHNHN N C - C1.36 Å C - C1.49 ÅC - C - C120˚ Simulated annealing und Molekülstrukturen

10 Parameter Position des MolekülsX,Y,Z Orientierung des Moleküls Θ freie Torsionswinkel 1, 2, 3, 4, 5, 6, 7 Molekül kann mittels interne Koordinaten beschrieben werden statt 17 x 3 = 51 Atomkoordinaten Total: 13 Simulated annealing und Molekülstrukturen N Cimetidine HNHNHNHN N S HNHNHNHN HNHNHNHN N

11 (6) Nachdem die vorgeschriebene AnzahlT reduziert "Moves" akzeptiert Kann auch andere Kriterien berücksichtigen z.B.Coulomb Potentiale (3) Strukturparameter modifizieren neu alt + m Δ alt (4) Neuer Figure-of-merit rechnen neu (2) Figure-of-merit (z.B. R-Wert) rechnen alt (5) < alt oder neu alt n < exp (-( neu - alt ) / T) (7) Zurück zu Schritt (3) optimierte Struktur optimierte Struktur Struktur chemisch sinnvoll m ist ein Zufallszahl zwischen 0 und 1 n ist ein Zufallszahl zwischen 0 und 1 ermöglicht Herauskommen aus falsche Minima Annealing Schema weniger Strukturen mit neu > alt akzeptiert sonst alt unverändert Simulated annealing und Molekülstrukturen (1) Start mit einem Satz Strukturparameter alt X,Y,Z, Θ,,, 1-n }

12 Reduce temperature yes no yes Prescribed number of moves reached? no Back to previous model Simulated Annealing no yes Is the model chemically reasonable? Move acceptable? Random variation of X, Y, Z, Θ,,, n Initial model SA control parameters Evaluate fitness Powder data

13 No.AtomDistanceAngle Ashift max min max B 1C1 2C2 3C3 4O4 5N5 6C6 7C7 8C8 9C9 (C) H C7H 3 || | | (C) = C1 - C2 – C3 – N5 – C6 – C8H 3 || | O4 C9H Å 1.50 Å 1.45 Å 1.33 Å1.53 Å 1.23 Å Polymer Clarifier

14 NoAtomDistanceAngle Ashift max min max B 1C1 2C21.39 Å1 3C3 4O4 5N5 6C6 7C7 8C8 9C9 Polymer Clarifier (C) H C7H 3 || | | (C) = C1 - C2 – C3 – N5 – C6 – C8H 3 || | O4 C9H Å 1.50 Å 1.45 Å 1.33 Å1.53 Å 1.23 Å

15 NoAtomDistanceAngle Ashift max min max B 1C1 2C21.39 Å1 3C31.50 Å120˚2 4O4 5N5 6C6 7C7 8C8 9C9 Polymer Clarifier (C) H C7H 3 || | | (C) = C1 - C2 – C3 – N5 – C6 – C8H 3 || | O4 C9H Å 1.50 Å 1.45 Å 1.33 Å1.53 Å 1.23 Å

16 NoAtomDistanceAngle Ashift max min max B 1C1 2C21.39 Å1 3C31.50 Å120˚2 4O41.23 Å120˚0˚3 5N5 6C6 7C7 8C8 9C9 Polymer Clarifier (C) H C7H 3 || | | (C) = C1 - C2 – C3 – N5 – C6 – C8H 3 || | O4 C9H Å 1.50 Å 1.45 Å 1.33 Å1.53 Å 1.23 Å

17 NoAtomDistanceAngle Ashift max min max B 1C1 2C21.39 Å1 3C31.50 Å120˚2 4O41.23 Å120˚0˚3 5N51.33 Å120˚180˚3 6C6 7C7 8C8 9C9 Polymer Clarifier (C) H C7H 3 || | | (C) = C1 - C2 – C3 – N5 – C6 – C8H 3 || | O4 C9H Å 1.50 Å 1.45 Å 1.33 Å1.53 Å 1.23 Å

18 NoAtomDistanceAngle Ashift max min max B 1C1 2C21.39 Å1 3C31.50 Å120˚2 4O41.23 Å120˚0˚3 5N51.33 Å120˚180˚3 6C61.45 Å120˚180˚5 7C7 8C8 9C9 Polymer Clarifier (C) H C7H 3 || | | (C) = C1 - C2 – C3 – N5 – C6 – C8H 3 || | O4 C9H Å 1.50 Å 1.45 Å 1.33 Å1.53 Å 1.23 Å

19 NoAtomDistanceAngle Ashift max min max B 1C1 2C21.39 Å1 3C31.50 Å120˚2 4O41.23 Å120˚0˚3 5N51.33 Å120˚180˚3 6C61.45 Å120˚180˚5 7C71.53 Å109.5˚60˚6 8C81.53 Å109.5˚180˚6 9C91.53 Å109.5˚300˚6 Polymer Clarifier (C) H C7H 3 || | | (C) = C1 - C2 – C3 – N5 – C6 – C8H 3 || | O4 C9H Å 1.50 Å 1.45 Å 1.33 Å1.53 Å 1.23 Å

20 NoAtomDistanceAngle Ashift max min max B 1C10 2C21.39 Å01 3C31.50 Å120˚02 4O41.23 Å120˚0˚13 5N51.33 Å120˚180˚3 6C61.45 Å120˚180˚5 7C71.53 Å109.5˚60˚6 8C81.53 Å109.5˚180˚6 9C91.53 Å109.5˚300˚6 Polymer Clarifier (C) H C7H 3 || | | (C) = C1 - C2 – C3 – N5 – C6 – C8H 3 || | O4 C9H Å 1.50 Å 1.45 Å 1.33 Å1.53 Å 1.23 Å

21 NoAtomDistanceAngle Ashift max min max B 1C10 2C21.39 Å01 3C31.50 Å120˚02 4O41.23 Å120˚0˚13 5N51.33 Å120˚180˚13 6C61.45 Å120˚180˚5 7C71.53 Å109.5˚60˚6 8C81.53 Å109.5˚180˚6 9C91.53 Å109.5˚300˚6 Polymer Clarifier (C) H C7H 3 || | | (C) = C1 - C2 – C3 – N5 – C6 – C8H 3 || | O4 C9H Å 1.50 Å 1.45 Å 1.33 Å1.53 Å 1.23 Å

22 NoAtomDistanceAngle Ashift max min max B 1C10 2C21.39 Å01 3C31.50 Å120˚02 4O41.23 Å120˚0˚13 5N51.33 Å120˚180˚13 6C61.45 Å120˚180˚25 7C71.53 Å109.5˚60˚6 8C81.53 Å109.5˚180˚6 9C91.53 Å109.5˚300˚6 Polymer Clarifier (C) H C7H 3 || | | (C) = C1 - C2 – C3 – N5 – C6 – C8H 3 || | O4 C9H Å 1.50 Å 1.45 Å 1.33 Å1.53 Å 1.23 Å

23 NoAtomDistanceAngle Ashift max min max B 1C10 2C21.39 Å01 3C31.50 Å120˚02 4O41.23 Å120˚0˚13 5N51.33 Å120˚180˚13 6C61.45 Å120˚180˚25 7C71.53 Å109.5˚60˚36 8C81.53 Å109.5˚180˚36 9C91.53 Å109.5˚300˚36 Polymer Clarifier (C) H C7H 3 || | | (C) = C1 - C2 – C3 – N5 – C6 – C8H 3 || | O4 C9H Å 1.50 Å 1.45 Å 1.33 Å1.53 Å 1.23 Å

24 NoAtomDistanceAngle Ashift max min max B 1C10 2C21.39 Å01 3C31.50 Å120˚02 4O41.23 Å120˚0˚15˚3 5N51.33 Å120˚180˚15˚3 6C61.45 Å120˚180˚21˚5 7C71.53 Å109.5˚60˚35˚6 8C81.53 Å109.5˚180˚35˚6 9C91.53 Å109.5˚300˚35˚6 Polymer Clarifier (C) H C7H 3 || | | (C) = C1 - C2 – C3 – N5 – C6 – C8H 3 || | O4 C9H Å 1.50 Å 1.45 Å 1.33 Å1.53 Å 1.23 Å

25 NoAtomDistanceAngle Ashift max min max B 1C10 2C21.39 Å01 3C31.50 Å120˚02 4O41.23 Å120˚0˚15˚0˚360˚3 5N51.33 Å120˚180˚15˚-180˚180˚3 6C61.45 Å120˚180˚21˚160˚200˚5 7C71.53 Å109.5˚60˚35˚30˚150˚6 8C81.53 Å109.5˚180˚35˚150˚270˚6 9C91.53 Å109.5˚300˚35˚-90˚30˚6 Polymer Clarifier (C) H C7H 3 || | | (C) = C1 - C2 – C3 – N5 – C6 – C8H 3 || | O4 C9H Å 1.50 Å 1.45 Å 1.33 Å1.53 Å 1.23 Å

26 NoAtomDistanceAngleA shift max τ min τ max B 1C1 2N2 3C3 4N4 5C5 6N6 7N7 8C8 9C9 10S Å 1.35 Å 1.51 Å 1.31 Å 1.34 Å 1.52 Å 1.81 Å 1.53 Å 1.47 Å 1.37 Å 1.32 Å 1.47 Å 1.36 Å 1.14 Å 1.34 Å

27 NoAtomDistanceAngleA shift max τ min τ max B 1C1 2N C N C N N C C S Å 1.35 Å 1.51 Å 1.31 Å 1.34 Å 1.52 Å 1.81 Å 1.53 Å 1.47 Å 1.37 Å 1.32 Å 1.47 Å 1.36 Å 1.14 Å 1.34 Å

28 NoAtomDistanceAngleA shift max τ min τ max B 1C1 2N C N C N N C C S Å 1.35 Å 1.51 Å 1.31 Å 1.34 Å 1.52 Å 1.81 Å 1.53 Å 1.47 Å 1.37 Å 1.32 Å 1.47 Å 1.36 Å 1.14 Å 1.34 Å

29 NoAtomDistanceAngleA shift max τ min τ max B 1C1 2N C N C N N C C S Å 1.35 Å 1.51 Å 1.31 Å 1.34 Å 1.52 Å 1.81 Å 1.53 Å 1.47 Å 1.37 Å 1.32 Å 1.47 Å 1.36 Å 1.14 Å 1.34 Å

30 NoAtomDistanceAngleA shift max τ min τ max B 1C1 2N C N ˚ C ˚ N N ˚ C ˚ C ˚ S ˚ Å 1.35 Å 1.51 Å 1.31 Å 1.34 Å 1.52 Å 1.81 Å 1.53 Å 1.47 Å 1.37 Å 1.32 Å 1.47 Å 1.36 Å 1.14 Å 1.34 Å

31 NoAtomDistanceAngleA shift max τ min τ max B 11C ˚180˚540˚10 12C ˚180˚540˚11 13N ˚0˚360˚12 14C N C C Å 1.35 Å 1.51 Å 1.31 Å 1.34 Å 1.52 Å 1.81 Å 1.53 Å 1.47 Å 1.37 Å 1.32 Å 1.47 Å 1.36 Å 1.14 Å 1.34 Å

32

33 Strukturparameter sind die Gene X,Y,Z, Θ,,, 1-n Satz von Strukturparameter ist ein Chromosom X,Y,Z, Θ,,, 1-n } X,Y,Z, Θ,,, 1-n } Start mit einem Anzahl verschieden Individuen Neue Generation erzeugt via Rekombination/Mutation Nur die "fittest" überleben Neue Generation erzeugt... Evolutionäre Algorithmen alternativer "global optimization" Verfahren

34 Evolutionäre Algorithmen - Prinzipien Parameterisierung Algorithmus zur Erzeugung eines "Phenotyps" Erzeugung einer Population möglicher Lösungen Rekombination/ Mutation Berechnung der individuellen Fitness "Survival of the fittest" R = 0.31R = 0.22 R = 0.25 R = 0.35 R = 0.22 R = 0.42 R = 0.3

35

36 Strukturlösung mittels Modelbau (Zufälliges) Modell vom Computer Modell optimieren Methode der Optimierung least-squares refinement simulated annealing evolutionary algorithm lokal Optimierung } global Optimierung

37 Least squares is like dropping a kangaroo somewhere on the surface of the earth, telling it to hop only uphill and hoping it will get to the top of mount Everest Least squares refinement Strukturlösung mittels Modelbau

38 Simulated Annealing is like doing the same, but getting the kangaroo very, very drunk first. Simulated annealing Strukturlösung mittels Modelbau

39 Genetic Algorithms are like taking a whole plane load of kangaroos and letting them reproduce freely (not pictured)... Genetic algorithms Strukturlösung mittels Modelbau

40 Genetic algorithms and regularly shooting those at lower altitudes. Note: no kangaroos were harmed in the making of this presentation Strukturlösung mittels Modelbau


Herunterladen ppt "Kristallchemie und Kristallstrukturdatenbanken Pulverdiffraktometrie Einkristall Strukturanalyse Strukturanalyse mittels Pulverdaten Kristallchemie in."

Ähnliche Präsentationen


Google-Anzeigen