History of spectroscopy
The history of spectroscopy began in the 17th century. New designs in optics, specifically prisms, enabled systematic observations of the solar spectrum. Isaac Newton first applied the word spectrum to describe the rainbow of colors that combine to form white light. During the early 1800s, Joseph von Fraunhofer conducted experiments with dispersive spectrometers that enabled spectroscopy to become a more precise and quantitative scientific technique. Since then, spectroscopy has played and continues to play a significant role in chemistry, physics and astronomy. Fraunhofer observed and measured dark lines in the Sun's spectrum.
Origins and experimental development
The Romans were already familiar with the ability of a prism to generate a rainbow of colors.Newton is traditionally regarded as the founder of spectroscopy, but he was not the first man of science who studied and reported on the solar spectrum. The works of Athanasius Kircher, Jan Marek Marci, Robert Boyle, and Francesco Maria Grimaldi, predate Newton's optics experiments.
Newton published his experiments and theoretical explanations of dispersion of light in his 'Opticks'. His experiments demonstrated that white light could be split up into component colors by means of a prism and that these components could be recombined to generate white light. He demonstrated that the prism is not imparting or creating the colors but rather separating constituent parts of the white light.
Newton's corpuscular theory of light was gradually succeeded by the wave theory. It was not until the 19th century that the quantitative measurement of dispersed light was recognized and standardized. As with many subsequent spectroscopy experiments, Newton's sources of white light included flames and stars, including our own sun. Subsequent studies of the nature of light include those of Hooke, Huygens, Young. Subsequent experiments with prisms provided the first indications that spectra were associated uniquely with chemical constituents. Scientists observed the emission of distinct patterns of colour when salts were added to alcohol flames.
Early 19th Century (1800 - 1829)
In 1802, William Hyde Wollaston built a spectrometer, improving on Newton's model, that included a lens to focus the Sun’s spectrum on a screen. Upon use, Wollaston realized that the colors were not spread uniformly, but instead had missing patches of colors, which appeared as dark bands in the sun's spectrum. At the time, Wollaston believed these lines to be natural boundaries between the colors, but this hypothesis was later ruled out in 1815 by Fraunhofer's work.Joseph von Fraunhofer made a significant experimental leap forward by replacing a prism with a diffraction grating as the source of wavelength dispersion. Fraunhofer built off the theories of light interference developed by Thomas Young, François Arago and Augustin-Jean Fresnel. He conducted his own experiments to demonstrate the effect of passing light through a single rectangular slit, two slits, and so forth, eventually developing a means of closely spacing thousands of slits to form a diffraction grating. The interference achieved by a diffraction grating both improves the spectral resolution over a prism and allows for the dispersed wavelengths to be quantified. Fraunhofer's establishment of a quantified wavelength scale paved the way for matching spectra observed in multiple laboratories, from multiple sources and with different instruments. Fraunhofer made and published systematic observations of the solar spectrum, and the dark bands he observed and specified the wavelengths of are still known as Fraunhofer lines.
Throughout the early 1800s, a number of scientists pushed the techniques and understanding of spectroscopy forward.
In the 1820s both John Herschel and William H. F. Talbot made systematic observations of salts using flame spectroscopy.
Mid 19th Century (1830 - 1869)
In 1835, Charles Wheatstone reported that different metals could be easily distinguished by the different bright lines in the emission spectra of their sparks, thereby introducing an alternative mechanism to flame spectroscopy.In 1849, J. B. L. Foucault experimentally demonstrated that absorption and emission lines appearing at the same wavelength are both due to the same material, with the difference between the two originating from the temperature of the light source.
In 1853, the Swedish physicist Anders Jonas Ångström presented observations and theories about gas spectra in his work Optiska Undersökningar to the Royal Swedish Academy of Sciences. Ångström postulated that an incandescent gas emits luminous rays of the same wavelength as those it can absorb. Ångström was unaware of Foucalt's experimental results. At the same time George Stokes and William Thomson were discussing similar postulates. Ångström also measured the emission spectrum from hydrogen later labeled the Balmer lines.
In 1854 and 1855, David Alter published observations on the spectra of metals and gases, including an independent observation of the Balmer lines of hydrogen.
The systematic attribution of spectra to chemical elements began in the 1860s with the work of German physicist Bunsen and Kirchhoff found that Fraunhofer lines correspond to emission spectral lines observed in laboratory light sources, and so they laid way for spectrochemical analysis in laboratory and astrophysics. Bunsen and Kirchhoff applied the optical techniques of Fraunhofer, Bunsen's improved flame source and a highly systematic experimental procedure to a detailed examination of the spectra of chemical compounds. They established the linkage between chemical elements and their unique spectral patterns. In the process, they established the technique of analytical spectroscopy. In 1860, they published their findings on the spectra of eight elements and identified these elements' presence in several natural compounds.
They demonstrated that spectroscopy could be used for trace chemical analysis and several of the chemical elements they discovered were previously unknown. Kirchhoff and Bunsen also definitively established the link between absorption and emission lines, including attributing solar absorption lines to particular elements based on their corresponding spectra. Kirchhoff went on to contribute fundamental research on the nature of spectral absorption and emission, including what is now known as Kirchhoff's Law of Thermal Radiation. Kirchhoff's applications of this law to spectroscopy are captured in three laws of spectroscopy:
- An incandescent solid, liquid or gas under high pressure emits a continuous spectrum.
- A hot gas under low pressure emits a "bright-line" or emission-line spectrum.
- A continuous spectrum source viewed through a cool, low-density gas produces an absorption-line spectrum.
August Beer observed a relationship between light absorption and concentration and created the color comparator which was later replaced by a more accurate device called the spectrophotometer.
Late 19th Century (1870 - 1899)
In the 19th century new developments such as the discovery of photography, Rowland's invention of the concave diffraction grating, and Schumann's works on discovery of vacuum ultraviolet made advance to shorter wavelengths very fast. At the same time Dewar observed series in alkali spectra, Hartley found constant wave-number differences, Balmer discovered a relation connecting wavelengths in the visible hydrogen spectrum, and finally Rydberg derived a formula for wave-numbers of spectral series.Johann Balmer discovered in 1885 that the four visible lines of hydrogen were part of a series that could be expressed in terms of integers. This was followed a few years later by the Rydberg formula, which described additional series of lines.
Meanwhile, the substantial summary of past experiments performed by Maxwell, resulted in his equations of electromagnetic waves.
In 1895, the German physicist Wilhelm Conrad Röntgen discovered and extensively studied X-rays, which were later used in X-ray spectroscopy. One year later, in 1896, French physicist Antoine Henri Becquerel discovered radioactivity, and Dutch physicist Pieter Zeeman observed spectral lines being split by a magnetic field.
Early 20th century (1900-1950)
The first decade of the 20th century brought the basics of quantum theory and interpretation of spectral series of hydrogen by Lyman in VUV and by Paschen in infrared. Ritz formulated the combination principle.In 1913 Bohr formulated his quantum mechanical model of atom. This stimulated empirical term analysis. Bohr published a theory of the hydrogen-like atoms that could explain the observed wavelengths of spectral lines due to electrons transitioning from different energy states. In 1937 "E. Lehrer created the first fully-automated spectrometer" to help more accurately measure spectral lines. With the development of more advanced instruments such as photo-detectors scientists were then able to more accurately measure specific wavelength absorption of substances.
Development of quantum mechanics
Between 1920 and 1930 fundamental concepts of quantum mechanics were developed by Pauli, Heisenberg, Schrödinger, and Dirac. Understanding of the spin and exclusion principle allowed conceiving how electron shells of atoms are filled with the increasing atomic number.Multiply ionized atoms
This branch of spectroscopy deals with radiation related to atoms that are stripped of several electrons. These are observed in very hot plasmas or in accelerator experiments. The lowest exited electron shells of such ions decay into stable ground states producing photons in VUV, EUV and soft X-ray spectral regions.Structure studies
Further progress in studies of atomic structure was in tight connection with the advance to shorter wavelength in EUV region. Millikan, Sawyer, Bowen used electric discharges in vacuum to observe some emission spectral lines down to 13 nm they prescribed to stripped atoms. In 1927 Osgood and Hoag reported on grazing incidence concave grating spectrographs and photographed lines down to 4.4 nm. Dauvillier used a fatty acid crystal of large crystal grating space to extend soft x-ray spectra up to 12.1 nm, and the gap was closed. In the same period Manne Siegbahn constructed a very sophisticated grazing incidence spectrograph that enabled Ericson and Edlén to obtain spectra of vacuum spark with high quality and to reliably identify lines of multiply ionized atoms up to O VI, with five stripped electrons. Grotrian developed his graphic presentation of energy structure of the atoms. Russel and Saunders proposed their coupling scheme for the spin-orbit interaction and their generally recognized notation for spectral terms.Accuracy
Theoretical quantum-mechanical calculations become rather accurate to describe the energy structure of some simple electronic configurations. The results of theoretical developments were summarized by Condon and Shortley in 1935.Edlén thoroughly analyzed spectra of MIA for many chemical elements and derived regularities in energy structures of MIA for many isoelectronic sequences. Spectra of rather high ionization stages were observed.
The most exciting event was in 1942, when Edlén proved the identification of some solar coronal lines on the basis of his precise analyses of spectra of MIA. This implied that the solar corona has a temperature of a million degrees, and strongly advanced understanding of solar and stellar physics.
After the WW II experiments on balloons and rockets were started to observe the VUV radiation of the Sun.. More intense research continued since 1960 including spectrometers on satellites.
In the same period the laboratory spectroscopy of MIA becomes relevant as a diagnostic tool for hot plasmas of thermonuclear devices which begun with building Stellarator in 1951 by Spitzer, and continued with tokamaks, z-pinches and the laser produced plasmas. Progress in ion accelerators stimulated beam-foil spectroscopy as a means to measure lifetimes of exited states of MIA. Many various data on highly exited energy levels, autoionization and inner-core ionization states were obtained.
Electron beam ion trap
Simultaneously theoretical and computational approaches provided data necessary for identification of new spectra and interpretation of observed line intensities. New laboratory and theoretical data become very useful for spectral observation in space. It was a real upheaval of works on MIA in USA, England, France, Italy, Israel, Sweden, Russia and other countriesA new page in the spectroscopy of MIA may be dated as 1986 with development of EBIT due to a favorable composition of modern high technologies such as cryogenics, ultra-high vacuum, superconducting magnets, powerful electron beams and semiconductor detectors. Very quickly EBIT sources were created in many countries.
A wide field of spectroscopic research with EBIT is enabled including achievement of highest grades of ionization, wavelength measurement, hyperfine structure of energy levels, quantum electrodynamic studies, ionization cross-sections measurements, electron-impact excitation CS, X-ray polarization, relative line intensities, dielectronic recombination CS, magnetic octupole decay, lifetimes of forbidden transitions, charge-exchange recombination, etc.