XANES

X-ray absorption near edge structure (XANES), also known as near edge X-ray absorption fine structure (NEXAFS), is a type of absorption spectroscopy that indicates the features in the X-ray absorption spectra (XAS) of condensed matter due to the photoabsorption cross section for electronic transitions from an atomic core level to final states in the energy region of 50–100 eV above the selected atomic core level ionization energy, where the wavelength of the photoelectron is larger than the interatomic distance between the absorbing atom and its first neighbour atoms. X-ray absorption near edge structure (XANES), also known as near edge X-ray absorption fine structure (NEXAFS), is a type of absorption spectroscopy that indicates the features in the X-ray absorption spectra (XAS) of condensed matter due to the photoabsorption cross section for electronic transitions from an atomic core level to final states in the energy region of 50–100 eV above the selected atomic core level ionization energy, where the wavelength of the photoelectron is larger than the interatomic distance between the absorbing atom and its first neighbour atoms. Both XANES and NEXAFS are acceptable terms for the same technique. XANES name was invented in 1980 by Antonio Bianconi to indicate strong absorption peaks in X-ray absorption spectra in condensed matter due to multiple scattering resonances above the ionization energy. The name NEXAFS was introduced in 1983 by Jo Stohr and is synonymous with XANES, but is generally used when applied to surface and molecular science. The fundamental phenomenon underlying XANES is the absorption of an x-ray photon by condensed matter with the formation of many body excited states characterized by a core hole in a selected atomic core level. (see the first Figure). In the single particle theory approximation, the system is separated into one electron in the core levels of the selected atomic species of the system and N-1 passive electrons. In this approximation the final state is described by a core hole in the atomic core level and an excited photoelectron. The final state has a very short life time because of the short life-time of the core hole and the short mean free path of the excited photoelectron with kinetic energy in the range around 20-50 eV. The core hole is filled either via an Auger process or by capture of an electron from another shell followed by emission of a fluorescent photon. The difference between NEXAFS and traditional photoemission experiments is that in photoemission, the initial photoelectron itself is measured, while in NEXAFS the fluorescent photon or Auger electron or an inelastically scattered photoelectron may also be measured. The distinction sounds trivial but is actually significant: in photoemission the final state of the emitted electron captured in the detector must be an extended, free-electron state. By contrast in NEXAFS the final state of the photoelectron may be a bound state such as an exciton since the photoelectron itself need not be detected. The effect of measuring fluorescent photons, Auger electrons, and directly emitted electrons is to sum over all possible final states of the photoelectrons, meaning that what NEXAFS measures is the total joint density of states of the initial core level with all final states, consistent with conservation rules. The distinction is critical because in spectroscopy final states are more susceptible to many-body effects than initial states, meaning that NEXAFS spectra are more easily calculable than photoemission spectra. Due to the summation over final states, various sum rules are helpful in the interpretation of NEXAFS spectra. When the x-ray photon energy resonantly connects a core level with a narrow final state in a solid, such as an exciton, readily identifiable characteristic peaks will appear in the spectrum. These narrow characteristic spectral peaks give the NEXAFS technique a lot of its analytical power as illustrated by the B 1s π* exciton shown in the second Figure. Synchrotron radiation has a natural polarization that can be utilized to great advantage in NEXAFS studies. The commonly studied molecular adsorbates have sigma and pi bonds that may have a particular orientation on a surface. The angle dependence of the x-ray absorption tracks the orientation of resonant bonds due to dipole selection rules. Soft x-ray absorption spectra are usually measured either through the fluorescent yield, in which emitted photons are monitored, or total electron yield, in which the sample is connected to ground through an ammeter and the neutralization current is monitored. Because NEXAFS measurements require an intense tunable source of soft x-rays, they are performed at synchrotrons. Because soft x-rays are absorbed by air, the synchrotron radiation travels from the ring in an evacuated beam-line to the end-station where the specimen to be studied is mounted. Specialized beam-lines intended for NEXAFS studies often have additional capabilities such as heating a sample or exposing it to a dose of reactive gas. In the absorption edge region of metals, the photoelectron is excited to the first unoccupied level above the Fermi level. Therefore, its mean free path in a pure single crystal at zero temperature is as large as infinite, and it remains very large, increasing the energy of the final state up to about 5 eV above the Fermi level. Beyond the role of the unoccupied density of states and matrix elements in single electron excitations, many-body effects appear as an 'infrared singularity' at the absorption threshold in metals. In the absorption edge region of insulators the photoelectron is excited to the first unoccupied level above the chemical potential but the unscreened core hole forms a localized bound state called core exciton. The fine structure in the x-ray absorption spectra in the high energy range extending from about 150 eV beyond the ionization potential is a powerful tool to determine the atomic pair distribution (i.e. interatomic distances) with a time scale of about 10−15 s.In fact the final state of the excited photoelectron in the high kinetic energy range (150-2000 eV ) is determined only by single backscattering events due to the low amplitude photoelectron scattering. In the NEXAFS region, starting about 5 eV beyond the absorption threshold, because of the low kinetic energy range (5-150 eV) the photoelectron backscattering amplitude by neighbor atoms is very large so that multiple scattering events become dominant in the NEXAFS spectra.