
1.2.3 X-Ray Crystallography
X-ray crystallography is a study of crystal structures through the use of x-ray diffraction
techniques. X rays are very suitable for this purpose because their wavelength in the 0.1 ˚A
(∼100 keV) to 1 ˚A (∼10 keV) range is of the order of typical crystalline lattice separations.
An x-ray beam striking a crystalline lattice is scattered by the spatial distribution of atomic
electrons and the imaged diffraction pattern provides information on the atomic or molecular
structure of the crystalline sample. In 1912 Max von Laue established the wave nature of x
rays and predicted that crystals exhibit diffraction phenomena.
Soon thereafter, William H. Bragg and William L. Bragg analyzed the crystalline structure
of sodium chloride, derived the Bragg relationship 2d sin φ = mλ (Fig. 1.8) linking the lattice
spacing d with x-ray wavelength λ, and laid the foundation for x-ray crystallography. The
crystal lattice of a sample acts as a diffraction grating and the interaction of x rays with the
atomic electrons creates a diffraction pattern which is related, through a Fourier transform, to
the electron spectral distribution in the sample under investigation.
Instrumentation for x-ray diffraction studies consists of a monoenergetic x-ray source, a
device to hold and rotate the crystal, and a detector suitable for measuring the positions and
intensities of the diffraction pattern.
Monoenergetic x rays are obtained by special filtration of x rays produced either by an x-ray
tube or from an electron synchrotron storage ring. The basic principles of modern x-ray
crystallography are essentially the same as those enunciated almost 100 years ago by von
Laue and the Braggs; however, the technique received a tremendous boost by incorporation of
computer technology after the 1970s, increasing significantly the accuracy and speed of the
technique.
1.2.4 X-Ray Spectroscopy
X-ray spectroscopy is an analytical technique for determination of elemental composition of
solid or liquid samples in many fields, such as material science, environmental science,
geology, biology, forensic science, and archaeometry.
The technique is divided into three related categories: the most common of them is the x-ray
absorption spectrometry (also called x-ray fluorescence spectrometry), and the other two are
x-ray photoelectron spectrometry and Auger spectrometry. All three techniques rely on
creation of vacancies in atomic shells of the various elements in the sample under study as
well as on an analysis of the effects that accompany the creation of vacancies (e.g., emission
of photoelectron, emission of characteristic line spectrum, and emission of Auger electron).
Like other practical emission spectroscopic methods, x-ray spectroscopy consists of three
steps:
1. Excitation of atoms in the sample to produce fluorescence emission lines (or
photoelectrons or Auger electrons) characteristic of the elements in the sample. The most
common means for exciting characteristic x-ray photons for the spectroscopic analysis is by