Journal of Structural Chemistry, Vol. 53, Supplement, pp.

S1-S3, 2012
Original Russian Text Copyright 2012 by S. V. Borisov, N. V. Podberezskaya

X-RAY DIFFRACTION ANALYSIS:

A BRIEF HISTORY AND ACHIEVEMENTS
OF THE FIRST CENTURY

S. V. Borisov and N. V. Podberezskaya UDC 548.0

The work presents the major stages of the development in single crystal X-ray diffraction analysis using the
Laue X-ray diffraction (discovered in 1912).
Keywords: diffraction, Laues discovery, history of development, XRD.

In June 8, 1912 during the meeting of the German Physical Society at the University of Berlin a thirty-three years
old physicist Max von Laue announced his discovery of X-ray diffraction in crystals as in a three-dimensional diffraction
grating [1]. Rapid development of physics in pre-war Europe provided the necessary background for this discovery which, in
turn, solved the problem of the nature of X-rays and sizes of atoms. Two English researchers W. H. Bragg and W. L. Bragg,
father and son, used the discovery to confirm Barlows hypothetic model of rock salt, thus initiating the first X-ray diffraction
analysis of single crystals [2, 3]. Braggs laboratory became the school and center for the development of this new method,
where many future structuralists acquired their skills and knowledge. The number of objects studied increased significantly
in 1916 after P. Debay and P. Scherrer had demonstrated how to analyze the structure of polycrystalline samples [4].
In Russia, the discovery of X-ray diffraction was particularly interesting for mineralogists. E. Fedorovs works on 230 space
groups of crystal symmetry (1891) was finally supported experimentally, which proved their perfect geometry. Apart from
being a crystallographer, Fedorov was also a mineralogist, petrographer, and chemist, which is likely why he reckoned that
only 127 groups could exist in nature, while the rest 103, called nonsymmorphic, could not occur in reality. One of the
earliest results of the diffraction method showed the opposite the nonsymmorphic groups were the most frequent.
Therefore, Fedorov had an opportunity to change his point of view while alive. In the USSR A. Fersman, an active and
celebrated mineralogist, realized the need to develop X-ray studies and found an extremely talented chemist to carry out these
experiments. Thus, since 1934 N. Belov plunged into structural mineralogy and translated several fundamental works by
foreign mineralogists and specialists in crystal chemistry into Russian [5]. At that time, crystal structures were mainly studied
in the Crystallograhy Laboratory in Moscow (later Institute of Crystallography of the USSR Academy of Sciences) and
Mineralogical Museum of Leningrad Mining Institute.
Since 1944 the laboratory of crystal structure of the Institute of Crystallography of the USSR Academy of Sciences
headed by N. Belov until his death in 1982 became the leading center for X-ray analysis in the USSR and had many branches
inside the Institute as well as in different cities and republics of the country [6].
One-time determinations of the structure of complex compounds performed manually no longer satisfied the needs
of both clients and researchers. With the advent of digital technologies a new goal was set automation of all stages of X-
ray analysis from the experiment to the resulting paper.

A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk;
borisov@niic.nsc.ru. Translated from Zhurnal Strukturnoi Khimii, Vol. 53, Supplement, pp. S5-S7, 2012. Original article
submitted February 22, 2012.

0022-4766/12/53 Supplement-0001 S1
 However, the phase problem, i.e. the uncertainty of the phases of the structure amplitudes Fhkl observed during the
diffraction, turned out to be a stumbling block. Thus, the international scientific community joined forces to solve this
problem. Within a decade (1948-1958) due to the efforts of physicists, mathematicians, and chemists new direct methods
were developed based on positive Fourier electron density with structure amplitudes as coefficients.
HarkerKasper inequalities (D. Harker and J. S. Kasper), statistical relations of phases by D. Sayre,
W. H. Zachariasen, W. Cochren, and other provided amplitude phases of the most intense X-ray reflections that were then
used to determine the phases of the next group of amplitudes. Developments of experimentalists were based on fundamental
mathematical calculations for phase relations (J. Karle, H. Hauptman, J. A. Goedkoop, and A. Kitaigorodsky). Gradual
upgrading of algorithms and programs for automatic determination of structures resulted in the creation of MULTAN
software, which spared the researchers laborious calculations and evaluations of variants [7-11].
Alongside statistical methods, crystal structures were sought to be determined using the Patterson function
calculated from the experiment. The minimization, variants of structures obtained by the superposition of the Patterson
functions shifted by an interatomic vector, was a popular method in structural crystallography in the middle of the 20th
century [12].
Hence, a laborious search for efficient methods of structure determination and experimental verification of ideas and
suggestions resulted in the establishment of an affective standard procedure (SHELX software developed by G. M. Sheldrick
that combined direct and Patterson methods of structure determination [13]), which did not require a modern user to know
this long history. Together with the advent of automatic diffractometers [14], it caused an immense stream of new structures.
Today structural databases contain hundreds of thousands of structures.
X-ray studies in the USSR kept pace with international advances in this field, despite the lack of equipment and
computers. In 1954, I. Rumanova (a researcher from Belovs laboratory) published a work on statistical determination of
phases of structural amplitudes using an original method of symmetry constraints [7]. In 1955, N. Golovastikov and N. Belov
showed a geometric interpretation of statistical relations of SayreZachariasenCochren phases [8]. In 1955,
A. Kitaigorodsky published a monograph on the theory of X-ray diffraction [11]; the Patterson function was also studied
extensively, which resulted in numerous works by researchers of the Institute of Crystallography, Gorky University, Institute
of Inorganic Chemistry of the Siberian Branch of the Academy of Sciences, Kishenev group, and Moscow State University
[15]; finally, Modern Crystallography encyclopedia in four volumes edited by B. Vainshtein was published [16].
There was a similar situation with the software for X-ray studies. F. Brusentsev, V. Dvoryankin, B. Schedrin,
A. Tovbis, and later V. Adrianov, etc. developed programs applying the method of least squares for soviet computers, which
ensured international quality of works [17].
Nowadays due to the efforts of the international scientific community (International Union of Crystallography) X-
ray analysis may be considered a well-organized physical method as there are numerous standard devices and programs, clear
criteria for assessing the quality of the results, multifunctional databases, specialized magazines, and regular international
conferences. This method is widely used all over the world. Thousands of new structures are determined every year, which
provides a vast primary material for crystallography, crystal chemistry, and quantum chemistry as well as for understanding
and modeling the organization of the matter at the atomic level. As the data show, most of the space symmetry groups
suggested by E. Fedorov can be found in both synthetic and natural crystals [18].
The diversity of nature was revealed in the existence of partially ordered objects (orderdisorder, K. Dornbergtr
Schiff) [19] and quasi crystals with unique properties, namely high-temperature superconductivity [20], a phenomenon
demonstrating the scantiness of our knowledge. Bismuth ferrite is yet another unique compound with exceptional magnetic
properties that has been studied for more than 50 years [21]. These exceptions are known to make scientific elites brainstorm.
Alternate searches often result in the need to change conventional concepts, and in many areas X-ray diffraction remains the
only objective method to verify new hypotheses.

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 In conclusion, we would like to note that we have made a brief analysis of the main stages in the development of
XRD, which was first discovered by Max von Laue. More detailed information may be obtained at the website of the
International Union of Crystallography (IUCr) and in works of our international colleagues [22-27].

REFERENCES

1. M. Laue, Aufstze und Vortrge [in Russian], L. S. Freiman (ed.), Nauka, Moscow (1969), pp. 211-222.
2. W. L. Bragg, Proc. Cambridge Philos. Soc., 17, 43-57 (1913).
3. W. L. Bragg, The Development of X-ray Analysis, Bell &Sons, London (1975).
4. P. Debay, P. Scherrer, and K. Nachr, Ges. Wiss. Gttingen Math. Physik., Kl, 1-26 (1916).
5. V. I. Simonov, Crystallography, 56, ed. 6, 965-968 (2011).
6. V. I. Simonov, Crystallography, 56, ed. 6, 968-974 (2011).
7. I. M. Rumanova, Reports of the USSR Academy of Sciences, 98, No. 3, 399-402 (1954).
8. N. I. Golovastikov and N. V. Belov, Reports of the USSR Academy of Sciences, 104, No. 4, 540-543 (1955).
9. V. I. Adrianov, in: Diffraction Methods for the Study of Compounds col. Papers, Shtiintza, Kishinev (1981), pp. 88-97.
10. M. Leddy and R. Palmer (eds.), Direct Methods in XRD (theory and practice) [Russian transl. by A. I. Karaulov],
B. K. Vainshtein (ed.), Mir, Moscow (1983).
11. A. I. Kitaigorodsky, Theory of Structural Analysis, Izd. AN SSSR, Moscow (1957).
12. M. Burger, Crystal Structure and Vector Space [Russian translation by Ye. N. Belova and V. I. Simonov],
N. V. Belov (ed.), Inostr. Lit-ra, Moscow (1961).
13. G. M. Sheldrick, SHELX97 Release 97-2, Univ. Gttingen, Germany (1998).
14. U. K. Gamilton, Russian Chemical Reviews, 41, ed. 3, 566-583 (1972).
15. S. V. Borisov, V. P. Golovachev, V. V. Ilyukhin, and E. A. Kuzmin, Symmetric Relations in the Patterson Function [in
Russian], Nauka, Novosibirsk (1981).
16. B. K. Vainshtein (ed.), in: Modern Crystallography, 4 vol., Nauka, Moscow (1979-1981).
17. F. A. Brusentsev, Crystallography, 8, ed. 1, 10-15 (1963).
18. V. S. Urusov and T. N. Nadezhina, J. Struct. Chem., 50, Supplement, 22-37 (2009).
19. K. Dornbergtr-Schiff and H. Grell-Niemann, Acta Crystallogr., 14, 167-177 (1961).
20. D. Nelson, M. Whittingham, and T. George (eds.), in: High-Temperature Superconductors, Mir, Moscow (1988).
21. A. M. Kalinkin and V. M. Skorikov, J. Neorg. Khim., 55, No. 11, 1903-1919 (2010).
22. Preface. Laue Centennial., Z. Kristallogr., 227, III-V (2012).
23. H. Kubbinga, Z. Kristallogr., 227, 1-26 (2012).
24. M. Eckert, Z. Kristallogr., 227, 27-35 (2012).
25. A. Authier, Z. Kristallogr., 227, 36-51 (2012).
26. D. E. Schwarzenbach, Z. Kristallogr., 227, 52-62 (2012).
27. I. H. O. Srensen, I. S. Schmidt, J. P. Wright, et al., Z. Kristallogr., 227, 63-78 (2012).

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