Volume 3 • Issue 4 • 1000e112
J Thermodynam Cat
ISSN: 2157-7544 JTC, an open access journal
Research Article Open Access
Datta, J Thermodynam Cat 2012, 3:4
DOI: 10.4172/2157-7544.1000e112
Editorial Open Access
A Century Plus of X-rays
Timir Datta*
Department of Physics and Astronomy, University of South Carolina, USA
*Corresponding author: Timir Datta, Department of Physics and Astronomy,
University of South Carolina, USA, Tel: 803-777-2075; E-mail: datta@physics.sc.edu
Received September 27, 2012; Accepted September 28, 2012; Published
October 03, 2012
Citation: Datta T (2012) A Century Plus of X-rays. J Thermodynam Cat 3: e112.
doi:10.4172/2157-7544.1000e112
Copyright: © 2012 Datta T. This is an open-access article distributed under the
terms of the Creative Commons Attribution License, which permits unrestricted
use, distribution, and reproduction in any medium, provided the original author and
source are credited.
As we approach the last quarter of the celebration of the
International Year of Crystallography [1] let me relate some of the
excitements and the developments that followed the epochal works
conducted in 1912 on both sides of the English Channel. I will conclude
with a tip of my Stetson to today’s champions who are keeping the fre
brightly lit well into the twenty-frst century.
X-ray techniques have played a pivotal catalytic role in catalysis
R&D. Te term “catalysis” was introduced by Brezelius in 1835. Later
W. Oswald’s defnition -catalyst as an agent that afects the reaction rate
without it being consumed in the process joined the lexicon especially,
following his Chemistry Nobel prize of 1909.
Te story of x-ray in materials starts at the University of Munich.
Where, upon learning from Ewald that the particles inside crystals
are regularly spaced by a distance of the order of 1/1000 of the wave
length of visible light, Max Laue opined, wave nature of x-rays will
be confrmed if upon passing a beam thorough a crystal interference
patterns can be produced.
True Laue learnt about lattice size from Ewald, but he was fully
aware that at least since the seventeenth century ideas about internal
periodicity in crystalline solids have been on record. For instance Laue
knew that in a new year’s pamphlet (1611) Kepler had remarked on
the symmetry of snowfakes. NB: Keppler also had the conviction
that the geometric solids polyhedrons are the universal building
blocks. 1669 Neils Stensen discovered that crystal faces intersect at
characteristic angles. Huygen related birefringence of calcite (1690)
to a particular 3-dimensional array of ellipsoidal particles. In 1773
Bergman and 1782 Hauy described crystals to be masonry of tiny
identical bricks. To accommodate thermal expansion and elasticity,
Seeber (1824) replaced the bricks by spherical molecules placed at
positions of equilibrium. Hassel’s classifcation of 32 types of crystals
in 1830 was followed by Franz Neumann’s (1833) suggestion that
crystal symmetries refect internal physics. Also Millerian indices
(1839) preceded the development of 14 translational lattices by Bravais
(1850). It is likely that most of this was common academic lore. But the
technology to physically test these ideas was not yet available. In 1895
Rontgen discovered x-rays serendipitously while researching electrical
discharges in vacuum but its nature and the associated wave length was
not immediately apparent.
When on a skiing expedition Laue discussed the idea with
Sommerfeld, Wien and others were prompt of raise doubts; but, shortly
Walter Friedrich set up an experiment and forthright succeeded in
photographing interference patterns by passing x-rays thru a copper
sulfate crystal. With this single epochal observation [2,3] the Munich
group resolved a whole array of fundamental questions namely, x-rays
are short wavelength (high energy) Maxwellian waves, “atoms” exist
and inside crystals they form an ordered lattices. However, it will still
be many more decades before the dust of atomicity will settle [4].
In Munich, the tremendous signifcance of the Laue spots must
have been clear right away. Because promptly before the publication of
the results pertaining to the discovery, Walter Friedrich, Paul Knipping
and Max Laue signed a one-page document stating “Te undersigned
are engaged since 21 April 1912 with experiments about interference
of x-rays passing through crystals”. It was deposited by Sommerfeld on
14 May 1912 [5].
As we know today, wave scattering by lattice determine many solid
state properties including all-important band structure. But the physics
of X-ray scattering in a crystal a la the Munich group was not quite
right. Te description was under constrained. Te Laue-Ewald formula
involved three integers each representing the order of interference
associated with the three directions of space. Tis full 3-dimensional
scheme conjured up an overabundance of spots. Fewer spots were
observed in the Laue pattern and missing spots were misinterpreted as
“random” gaps in the incident x-ray spectrum.
Lucky for us, at the same time on the other side of the English
Channel a bright young chap, William Lawrence Bragg was taking his
National sciences (physics) degree at Cambridge University. His father
William Henry Bragg, physics professor at Leeds was aware of the
work at Munich and discussed the results with him. Mathematically
gifed Lawrence was intrigued by the absence of spots, the changing of
shapes from circular to oval as the pattern moved of incidence and also
that the pattern turned six degree when a crystal was rotated by just
half that angle. Typically, the angular displacements of non-specular
interference spots are determined by trigonometric functions and
produce highly nonlinear response [6]. Lawrence then barely 22 years
old fgured that the Laue pattern could not be due to three dimensional
lattices but a sub-set associated with interference of x-ray wavelets
refecting of successive atomic planes.
In this specular refection process there are (only) two relevant
lengths, the x-ray wave length θ and the inter-plane distance d(klm)
where klm are the Miller indices and the scattering angle (θ). Lawrence
Bragg derived the appropriate conditions for constructive interference
and obtained a simple eponymous equation that relates the order of the
interference (n) and the ratio of the lengths with sin (θ);
n
*
[λ/d(klm)] = 2
*
Sin(θ).
Furthermore based on this equation and the missing spots in the
Munich Lawrence was able to deduce that the lattice of ZnS is not
simple cubic (SC) as presumed by Laue et al but face centered cubic
(FCC). Not coincidentally William Barlow another Englishman was
the frst to introduce SC and FCC and the concept of close packing into
crystallography (1833). Shortly thereafer Lawrence lef Cambridge
to join his father at Leeds. At Leeds their roles can be best described
by a phrase from P.W. Anderson (Nobel Physics 1977) “theory on
Journal of
Thermodynamics & Catalysis
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ISSN: 2157-7544