simple Grotrian diagram showing electron transitions in a multi-electron atomAtomic spectroscopy exploits different energetic transitions experienced by atoms that are associated with either the absorption or emission of photons. When these transitions involve the excitation and relaxation of the valence (outer or bonding) shell electrons of metal atoms and ions, the corresonding photons have energies within the ultraviolet and visible regions of the spectrum. A good example of this is the dark absorption lines in the solar spectrum, which are caused by heavier elements present in the outer layers of the sun.

The figure on the right shows a high energy photon with Ephoton = being absorbed, resulting in a 2s→3s electron excitation; similarly, a 3d→3p electron relaxation results in the emission of a lower energy photon. By convention, the change in electron energy ΔE = EfEi, where f and i refer to the final and initial states, respectively; so ΔE = Ephoton, and the sign of Ephoton tells you whether the photon is being absorbed or emitted. Since Ef and Ei depend on the number electrons and protons within an atom (or monatomic ion), the wavelengths associated with atomic absorption and emission are considered characteristic for a particular element.

Absorption and Emission:

In atomic absorption (AA) spectroscopy, absorption of a photon results in excitation of an electron from a lower to higher energy atomic orbital (AO). An instrument measures the absorbance, A, which is defined as the logarithm of the ratio of incident to transmitted radiant power of the photon beam, A = log(P0 ÷ P), at a wavelength specific to the element of interest. Samples are typically analysed using a flame atomic absorption spectrophotometer.

In atomic emission (AE) spectroscopy, thermal or electrical energy from an arc, flame, spark, or plasma is used to excite and electron from a lower to higher energy AO; when the excited electron returns to its original AO (i.e. the ground state), it may do so by emitting a photon. The instrument measures the intensity, I, of these emitted photons as a function of wavelength.

Because AO energies are well-defined, atomic absorption and emission spectra consist of discrete, narrow lines. This allows the concentration of metallic elements in different samples to be determined selectively, with lower limits at or below 1 mg/L (1 ppm). Techniques such as graphite furnace atomic absorption spectrophotometry (GFAAS) allow concentration to be measured down to µg/L (ppb) levels. Actual limits-of-detection vary with both element, technique, and sample matrix.