1.2 Historical development of crystallography

Crystallography's journey from ancient observations to cutting-edge science is a tale of curiosity and innovation. Early thinkers laid the groundwork, but it was the discovery of X-ray diffraction that truly revolutionized the field.

The 20th century saw crystallography evolve into a powerful tool for understanding matter at the atomic level. From unraveling DNA's structure to studying materials under extreme conditions, it's become essential in fields from biology to materials science.

Crystallography's Historical Development

Early Observations and Foundational Concepts

Top images from around the web for Early Observations and Foundational Concepts

• 

  Crystal Lattices View original

  Is this image relevant?

• 

  Lattice Structures in Crystalline Solids | Chemistry View original

  Is this image relevant?

• 

  Lattice Structures in Crystalline Solids | Chemistry for Majors View original

  Is this image relevant?

• 

  Crystal Lattices View original

  Is this image relevant?

• 

  Lattice Structures in Crystalline Solids | Chemistry View original

  Is this image relevant?

1 of 3

Top images from around the web for Early Observations and Foundational Concepts

• 

  Crystal Lattices View original

  Is this image relevant?

• 

  Lattice Structures in Crystalline Solids | Chemistry View original

  Is this image relevant?

• 

  Lattice Structures in Crystalline Solids | Chemistry for Majors View original

  Is this image relevant?

• 

  Crystal Lattices View original

  Is this image relevant?

• 

  Lattice Structures in Crystalline Solids | Chemistry View original

  Is this image relevant?

1 of 3

• Ancient Greek philosophers (Plato, Aristotle) made early observations on regular crystal shapes laid foundation for future studies
• Johannes Kepler published "The Six-Cornered Snowflake" in 1611 proposed hexagonal symmetry of snowflakes resulted from regular packing of water particles
• Nicolas Steno formulated Law of Constancy of Interfacial Angles in 1669 stated angles between corresponding crystal faces remain constant for given species
• René Just Haüy developed concept of "integrant molecule" in 1784 proposed crystals built from identical structural units
  • Introduced idea of crystal lattices
  • Explained crystal cleavage based on arrangement of structural units

Breakthrough Discoveries in the 20th Century

• Max von Laue discovered X-ray diffraction by crystals in 1912 provided first experimental proof of periodic atomic structure in crystals
  • Demonstrated wave nature of X-rays
  • Confirmed long-held hypothesis about internal structure of crystals
• X-ray crystallography development in early 20th century revolutionized field enabled determination of atomic positions within crystal structures
  • Allowed visualization of atomic arrangements in three dimensions
  • Provided insights into chemical bonding and material properties
• Neutron diffraction advent in 1940s expanded crystallographic techniques
  • Enabled study of magnetic structures (ferromagnetic materials)
  • Facilitated investigation of light elements (hydrogen in organic compounds)
  • Complemented X-ray diffraction for more comprehensive structural analysis

Key Figures in Crystallography

Pioneers of X-ray Crystallography

• Max von Laue demonstrated X-ray diffraction by crystals proved wave nature of X-rays and periodic atomic structure of crystals
  • Awarded Nobel Prize in Physics in 1914 for this discovery
• William Henry Bragg and William Lawrence Bragg developed Bragg's Law related wavelength of incident radiation to spacing between atomic planes in crystal
  • Formulated as $n\lambda = 2d\sin\theta$ where n is an integer, λ is wavelength, d is interplanar spacing, and θ is angle of incidence
• Braggs pioneered X-ray diffraction use to determine crystal structures solved structures of simple inorganic compounds (sodium chloride, diamond)
  • Received Nobel Prize in Physics in 1915 for their work

Contributors to Biological Crystallography

• Rosalind Franklin's X-ray diffraction work on DNA crucial in elucidating double helix structure contributed significantly to molecular biology and structural biochemistry
  • Produced famous "Photo 51" X-ray diffraction image of DNA
  • Her work was instrumental in Watson and Crick's DNA model
• Dorothy Hodgkin advanced protein crystallography determined structures of complex biological molecules (insulin, vitamin B12, penicillin)
  • Developed techniques for analyzing large, complex molecules
  • Awarded Nobel Prize in Chemistry in 1964 for her work

Theoretical and Methodological Innovators

• Linus Pauling applied quantum mechanics to crystallography developed theory of chemical bond and predicted structures of complex silicate minerals
  • Introduced concept of resonance in chemical bonding
  • Received Nobel Prize in Chemistry in 1954 for his work on chemical bonding
• John Desmond Bernal expanded crystallography application to biological molecules laid groundwork for structural biology
  • Pioneered use of X-ray crystallography in studying viruses and proteins
  • Developed methods for keeping biological samples hydrated during analysis

Technological Advancements in Crystallography

Improvements in X-ray Sources and Detectors

• X-ray tubes development with higher intensity and focus allowed study of smaller crystals and more complex structures
  • Rotating anode X-ray tubes increased X-ray flux by factor of 10
  • Microfocus X-ray sources enabled analysis of microcrystals (< 10 μm)
• Area detectors introduction (image plates, charge-coupled devices) greatly increased speed and efficiency of data collection
  • Reduced data collection time from days to hours or minutes
  • Improved signal-to-noise ratio and dynamic range

Advanced Radiation Sources and Techniques

• Synchrotron radiation sources provided extremely intense and tunable X-ray beams enabled study of microcrystals and time-resolved experiments
  • Brilliance up to 10^12 times greater than laboratory X-ray sources
  • Allowed for high-resolution studies of protein dynamics
• Cryocrystallography techniques advent allowed study of radiation-sensitive biological samples by reducing radiation damage
  • Samples cooled to around 100 K using liquid nitrogen
  • Extended crystal lifetime in X-ray beam by factor of 70 or more

Computational Advancements

• Computer modeling and simulation techniques (molecular dynamics, density functional theory) complemented experimental methods in understanding crystal structures and properties
  • Enabled prediction of crystal structures from chemical composition
  • Facilitated interpretation of experimental data and property calculations
• Direct methods and Patterson techniques development for phase determination greatly accelerated process of structure solution
  • Overcame phase problem in crystallography
  • Allowed for automated structure determination of small molecules
• Data processing software and automated structure refinement programs advancements significantly reduced time required for structure determination
  • Programs like SHELX and PHENIX streamlined crystallographic analysis
  • Enabled high-throughput structure determination in structural genomics projects

Impact of Crystallographic Techniques

Evolution of Diffraction Methods

• Transition from photographic film to electronic detectors in X-ray diffraction experiments dramatically improved data quality and collection speed
  • Increased sensitivity and dynamic range
  • Enabled real-time monitoring of diffraction patterns
• Single-crystal neutron diffraction techniques development allowed precise localization of hydrogen atoms and study of magnetic structures
  • Complemented X-ray diffraction for complete structural characterization
  • Provided insights into hydrogen bonding networks in materials
• Powder diffraction methods evolved to allow structure determination from polycrystalline samples expanded range of studiable materials
  • Rietveld refinement method enabled accurate structure determination from powder data
  • Applications in pharmaceuticals, ceramics, and metallurgy

Emerging Crystallographic Techniques

• Electron crystallography introduction enabled study of nanocrystalline materials and 2D crystals (graphene)
  • Allowed structure determination of beam-sensitive materials
  • Provided atomic-resolution imaging of surfaces and interfaces
• High-pressure crystallography techniques advances provided insights into material behavior under extreme conditions relevant to geophysics and materials science
  • Diamond anvil cells allowed studies at pressures up to 300 GPa
  • Revealed new high-pressure phases of common materials (ice, silica)
• Crystallography combination with spectroscopic techniques (Raman spectroscopy, X-ray absorption spectroscopy) allowed more comprehensive understanding of crystal structures and properties
  • Provided information on chemical bonding and electronic structure
  • Enabled in situ studies of materials under various conditions
• Serial femtosecond crystallography development using X-ray free-electron lasers opened new possibilities for studying radiation-sensitive samples and capturing ultrafast structural changes
  • Allowed "diffraction before destruction" of biological samples
  • Enabled time-resolved studies with femtosecond resolution