Physical Methods in Inorganic Chemistry First Half: Crystallography Textbooks



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5.068: Physical Methods in Inorganic Chemistry

First Half: Crystallography

Textbooks:

• W. Massa / R. Gould: Crystal Structure Determination.

(Springer)

• C. Giacovazzo (Ed.): Fundamentals of Crystallography

(Oxford University Press)

• L. Bragg (Ed.): The Crystalline State (4 volumes)

(Cornell University Press)

• Kleber / Bausch / Bohm: Einführung in die 

Kristallographie (Verlag Technik)



Crystallography: Strengths and Weaknesses

Strengths:

• Complete 3D structure with almost no assumptions.

• No size limitations (M > 10

7

)

• Fast



Weaknesses:

• You need a crystal.

• Average over space and time (no dynamics).

• Esp. for very large molecules: resolution often rather low.




X-Ray Crystallography: The Early Days

Wilhelm Conrad Röntgen (1845-1923)

1895: X-Rays (Nobel Prize 1901)

Born in Lennep (now Remscheid), Germany. Studied 

physics at the Polytechnic in Zürich.

Prof. for physics in Strassbourg (1876-79), Giessen

(1879-88), Würzburg (1888-1900), München (1900-20).

Research on elasticity, capillary action, specific heats, 

heat conduction in crystals, piezoelectricity, etc.

1895, while experimenting with electric current in an evacuated glass tube, he 

saw fluorescence of barium platinocyanide and figured that rays of some kind 

must be traveling across the room.

More experiments followed. X-rays go through paper, wood, aluminum, they 

blacken photo plates and do not show properties of light like reflection or 

refraction. X-ray photographs of his wife’s hand.

1901 first Nobel Prize for physics to W. C. Röntgen.




X-Ray Crystallography: The Early Days

Max Theodor Felix von Laue (1879-1960)

1912: X-Ray Diffraction (Nobel Prize 1914)

Born in Pfaffendorf, Germany. Studied physics in 

Strassbourg, Göttingen, München and Berlin

Prof. for physics in Zürich (1912-14), Frankfurt (1914-16), 

Würzburg (1916-19), Berlin (1919-43), Director MPI for 

Physical Chemistry in Berlin (1951-1958).

In order to prove that X-rays were actually electromagnetic

waves, he wanted to produce some kind of interference. His then more famous 

colleagues Sommerfeld and Wien thought it would never work, but Walter 

Friedrich (one of Sommerfeld’s assistants) and Paul Knipping tried it (with 

CuSO

4

) and succeeded after a while.



Laue worked out the mathematics and the whole thing was published in 1912.

1914 Nobel Prize for physics to M. von Laue.




X-Ray Crystallography: The Early Days

(William) Lawrence Bragg (1890-1971)

1912: Bragg law (Nobel Prize 1915)

Born in Adelaide, Australia. Son of the Englishman William 

(Henry) Bragg (1862-1942). 1909 he came to Engand with 

his father and started to study physics at Trinity College in 

Cambridge.

Lecturer at Trinity College, Cambridge (1914-19) and Prof. 

for physics in Manchester (1919-37), director of the National 

Physical Laboratory (1937-38), Prof. for experimental 

physics in Cambridge (1938-53) and Chairman of the 

Frequency Advisory Committee (1958-60).

Inspired by the work of M. von Laue, Lawrence Bragg, a grad student then, came 

up with                       . Using the first diffractometer, built by W. H. Bragg to 

measure the wavelength of X-Rays, the two Braggs determined the crystal 

structures of NaCl and other compounds.

1915 Nobel Prize for physics to W. L. Bragg (then 25 years old) and W. H. Bragg.

Θ

=



sin

2d



n

λ



Nobel Prizes for X-Ray Crystallography

1901: N.P. in Physics to Wilhelm Conrad Röntgen. Discovery of X-rays. 



1914: N.P. in Physics to Max Theodor Felix von Laue. X-ray diffraction.

1915: N.P. in Physics to William Henry Bragg & William Lawrence Bragg. 



Bragg law and crystal structures. 

1962: N.P. in Chemistry to Max Perutz & John Cowdery Kendrew. 



Structures of Hemoglobin and Myoglobin (isomorphous replacement). 

1962: N.P. in Medicine to James Dewey Watson, Francis Harry Compton 



Crick & Maurice Hugh Frederick Wilkins (Rosalind Franklin). Structure of 

DNA from fiber diffraction.

1964: N.P. in Chemistry to Dorothy Crowfoot Hodgkin. Crystal structure of 



vitamin B

12

.



1976: N.P. in Chemistry to William Nunn Lipscomb Jr. Structures and 

bonding conditions of Boranes.

1985: N.P. in Chemistry to Herbert Aaron Hauptman & Jerome Karle



(Isabella Karle). Direct Methods.

1988: N.P in Chemistry to Johann Deisenhofer, Robert Huber & Hartmut



Michel. Structure of bacteriorhodopsin (a photosynthetic reaction center). 


A Line of Descent in X-Ray Crystallography

Roscoe Dickinson

Hexamethylenetetramine 

(1923) 


Wilhelm Bragg (dad)

Lawrence Bragg (son)

John Bernal

Peter Müller



Your Name Here

Lalor Burdick

Chalcopyrite (1916)

Max Perutz & John Kendrew

Hemoglobin & myoglobin (1938-60)

Dorothy Hodgkin

Vitamin B

12

(1956)



Francis Crick & James Watson

Structure of DNA, (1953) 

NaCl, KCl (1912)

Rosalind Franklin,

George Sheldrick

SHELX, 


direct methods 

Linus Pauling

Secondary structure of 

proteins, (1951) 

Richard Dickerson & Dough Rees

Membrane 

proteins 

DNA/RNA


structures 

David Eisenberg 

3D domain

swapping 

tobacco mosaic 

virus (1953-58)

Twinning,

symmetry 



& Todd Yeates


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