Spectroscopy

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An example of spectroscopy: a prism analyses white light by dispersing it into its component colors. Light dispersion of a mercury-vapor lamp with a flint glass prism IPNrdeg0125.jpg
An example of spectroscopy: a prism analyses white light by dispersing it into its component colors.

Spectroscopy is the study of the interaction between matter and electromagnetic radiation as a function of the wavelength or frequency of the radiation. [1] [2] [3] [4] [5] [6] In simpler terms, spectroscopy is the precise study of color as generalized from visible light to all bands of the electromagnetic spectrum; indeed, historically, spectroscopy originated as the study of the wavelength dependence of the absorption by gas phase matter of visible light dispersed by a prism. Matter waves and acoustic waves can also be considered forms of radiative energy, and recently gravitational waves have been associated with a spectral signature in the context of the Laser Interferometer Gravitational-Wave Observatory (LIGO).

Contents

Spectroscopy, primarily in the electromagnetic spectrum, is a fundamental exploratory tool in the fields of physics, chemistry, and astronomy, allowing the composition, physical structure and electronic structure of matter to be investigated at the atomic, molecular and macro scale, and over astronomical distances. Important applications arise from biomedical spectroscopy in the areas of tissue analysis and medical imaging.

Introduction

Spectroscopy and spectrography are terms used to refer to the measurement of radiation intensity as a function of wavelength and are often used to describe experimental spectroscopic methods. Spectral measurement devices are referred to as spectrometers, spectrophotometers, spectrographs or spectral analyzers.

Daily observations of color can be related to spectroscopy. Neon lighting is a direct application of atomic spectroscopy. Neon and other noble gases have characteristic emission frequencies (colors). Neon lamps use collision of electrons with the gas to excite these emissions. Inks, dyes and paints include chemical compounds selected for their spectral characteristics in order to generate specific colors and hues. A commonly encountered molecular spectrum is that of nitrogen dioxide. Gaseous nitrogen dioxide has a characteristic red absorption feature, and this gives air polluted with nitrogen dioxide a reddish-brown color. Rayleigh scattering is a spectroscopic scattering phenomenon that accounts for the color of the sky.

Spectroscopic studies were central to the development of quantum mechanics and included Max Planck's explanation of blackbody radiation, Albert Einstein's explanation of the photoelectric effect and Niels Bohr's explanation of atomic structure and spectra. Spectroscopy is used in physical and analytical chemistry because atoms and molecules have unique spectra. As a result, these spectra can be used to detect, identify and quantify information about the atoms and molecules. Spectroscopy is also used in astronomy and remote sensing on Earth. Most research telescopes have spectrographs. The measured spectra are used to determine the chemical composition and physical properties of astronomical objects (such as their temperature and velocity).

Theory

One of the central concepts in spectroscopy is a resonance and its corresponding resonant frequency. Resonances were first characterized in mechanical systems such as pendulums. Mechanical systems that vibrate or oscillate will experience large amplitude oscillations when they are driven at their resonant frequency. A plot of amplitude vs. excitation frequency will have a peak centered at the resonance frequency. This plot is one type of spectrum, with the peak often referred to as a spectral line, and most spectral lines have a similar appearance.

In quantum mechanical systems, the analogous resonance is a coupling of two quantum mechanical stationary states of one system, such as an atom, via an oscillatory source of energy such as a photon. The coupling of the two states is strongest when the energy of the source matches the energy difference between the two states. The energy E of a photon is related to its frequency ν by E = where h is Planck's constant, and so a spectrum of the system response vs. photon frequency will peak at the resonant frequency or energy. Particles such as electrons and neutrons have a comparable relationship, the de Broglie relations, between their kinetic energy and their wavelength and frequency and therefore can also excite resonant interactions.

Spectra of atoms and molecules often consist of a series of spectral lines, each one representing a resonance between two different quantum states. The explanation of these series, and the spectral patterns associated with them, were one of the experimental enigmas that drove the development and acceptance of quantum mechanics. The hydrogen spectral series in particular was first successfully explained by the Rutherford–Bohr quantum model of the hydrogen atom. In some cases spectral lines are well separated and distinguishable, but spectral lines can also overlap and appear to be a single transition if the density of energy states is high enough. Named series of lines include the principal, sharp, diffuse and fundamental series.

Classification of methods

A huge diffraction grating at the heart of the ultra-precise ESPRESSO spectrograph. A Taste of ESPRESSO.jpg
A huge diffraction grating at the heart of the ultra-precise ESPRESSO spectrograph.

Spectroscopy is a sufficiently broad field that many sub-disciplines exist, each with numerous implementations of specific spectroscopic techniques. The various implementations and techniques can be classified in several ways.

Type of radiative energy

The types of spectroscopy are distinguished by the type of radiative energy involved in the interaction. In many applications, the spectrum is determined by measuring changes in the intensity or frequency of this energy. The types of radiative energy studied include:

Nature of the interaction

The types of spectroscopy also can be distinguished by the nature of the interaction between the energy and the material. These interactions include: [5]

Type of material

Spectroscopic studies are designed so that the radiant energy interacts with specific types of matter.

Atoms

Atomic spectroscopy was the first application of spectroscopy developed. Atomic absorption spectroscopy and atomic emission spectroscopy involve visible and ultraviolet light. These absorptions and emissions, often referred to as atomic spectral lines, are due to electronic transitions of outer shell electrons as they rise and fall from one electron orbit to another. Atoms also have distinct x-ray spectra that are attributable to the excitation of inner shell electrons to excited states.

Atoms of different elements have distinct spectra and therefore atomic spectroscopy allows for the identification and quantitation of a sample's elemental composition. After inventing the spectroscope, Robert Bunsen and Gustav Kirchhoff discovered new elements by observing their emission spectra. Atomic absorption lines are observed in the solar spectrum and referred to as Fraunhofer lines after their discoverer. A comprehensive explanation of the hydrogen spectrum was an early success of quantum mechanics and explained the Lamb shift observed in the hydrogen spectrum, which further led to the development of quantum electrodynamics.

Modern implementations of atomic spectroscopy for studying visible and ultraviolet transitions include flame emission spectroscopy, inductively coupled plasma atomic emission spectroscopy, glow discharge spectroscopy, microwave induced plasma spectroscopy, and spark or arc emission spectroscopy. Techniques for studying x-ray spectra include X-ray spectroscopy and X-ray fluorescence.

Molecules

The combination of atoms into molecules leads to the creation of unique types of energetic states and therefore unique spectra of the transitions between these states. Molecular spectra can be obtained due to electron spin states (electron paramagnetic resonance), molecular rotations, molecular vibration, and electronic states. Rotations are collective motions of the atomic nuclei and typically lead to spectra in the microwave and millimeter-wave spectral regions. Rotational spectroscopy and microwave spectroscopy are synonymous. Vibrations are relative motions of the atomic nuclei and are studied by both infrared and Raman spectroscopy. Electronic excitations are studied using visible and ultraviolet spectroscopy as well as fluorescence spectroscopy.

Studies in molecular spectroscopy led to the development of the first maser and contributed to the subsequent development of the laser.

Crystals and extended materials

The combination of atoms or molecules into crystals or other extended forms leads to the creation of additional energetic states. These states are numerous and therefore have a high density of states. This high density often makes the spectra weaker and less distinct, i.e., broader. For instance, blackbody radiation is due to the thermal motions of atoms and molecules within a material. Acoustic and mechanical responses are due to collective motions as well. Pure crystals, though, can have distinct spectral transitions, and the crystal arrangement also has an effect on the observed molecular spectra. The regular lattice structure of crystals also scatters x-rays, electrons or neutrons allowing for crystallographic studies.

Nuclei

Nuclei also have distinct energy states that are widely separated and lead to gamma ray spectra. Distinct nuclear spin states can have their energy separated by a magnetic field, and this allows for nuclear magnetic resonance spectroscopy.

Other types

Other types of spectroscopy are distinguished by specific applications or implementations:

Applications

UVES is a high-resolution spectrograph on the Very Large Telescope. UVES on UT2-KUEYEN.jpg
UVES is a high-resolution spectrograph on the Very Large Telescope.

There are several applications to spectroscopy in the field of medicine, physics, chemistry, and astronomy. Taking advantage of the properties of absorbance, spectroscopy can be used to identify certain states of nature. Such examples include:

History

The history of spectroscopy began with Isaac Newton's optics experiments (1666–1672). According to Andrew Fraknoi and David Morrison, "In 1672, in the first paper that he submitted to the Royal Society, Isaac Newton described an experiment in which he permitted sunlight to pass through a small hole and then through a prism. Newton found that sunlight, which looks white to us, is actually made up of a mixture of all the colors of the rainbow." [19] Newton applied the word "spectrum" to describe the rainbow of colors that combine to form white light and that are revealed when the white light is passed through a prism.

Fraknoi and Morrison state that "In 1802, William Hyde Wollaston built an improved spectrometer 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 spectrum." [19] During the early 1800s, Joseph von Fraunhofer made experimental advances 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. Per Fraknoi and Morrison, "Later, in 1815, German physicist Joseph Fraunhofer also examined the solar spectrum, and found about 600 such dark lines (missing colors), are now known as Fraunhofer lines, or Absorption lines." [19] [ better source needed ]

See also

Notes

  1. H. W. Kroto, Molecular Rotation Spectra, Wiley, New York, 1975 (Reprinted by Dover 1992)
  2. Philip R. Bunker and Per Jensen, Molecular Symmetry and Spectroscopy, NRC Research Press, Ottawa, 1998 ISBN   9780660196282
  3. D. Papoušek and M. R. Aliev, Molecular Vibrational-Rotational Spectra Elsevier, Amsterdam, 1982
  4. E. B. Wilson, J. C. Decius, and P. C. Cross, Molecular Vibrations, McGraw-Hill, New York, 1955 (Reprinted by Dover 1980)
  5. 1 2 Crouch, Stanley; Skoog, Douglas A. (2007). Principles of instrumental analysis. Australia: Thomson Brooks/Cole. ISBN   978-0-495-01201-6.
  6. Herrmann, R.; C. Onkelinx (1986). "Quantities and units in clinical chemistry: Nebulizer and flame properties in flame emission and absorption spectrometry (Recommendations 1986)". Pure and Applied Chemistry. 58 (12): 1737–1742. doi:10.1351/pac198658121737. S2CID   96002955.
  7. "A Taste of ESPRESSO" . Retrieved 15 September 2015.
  8. Mariani, Z.; Strong, K.; Wolff, M.; Rowe, P.; Walden, V.; Fogal, P. F.; Duck, T.; Lesins, G.; Turner, D. S.; Cox, C.; Eloranta, E.; Drummond, J. R.; Roy, C.; Turner, D. D.; Hudak, D.; Lindenmaier, I. A. (2012). "Infrared measurements in the Arctic using two Atmospheric Emitted Radiance Interferometers". Atmospheric Measurement Techniques. 5 (2): 329–344. Bibcode:2012AMT.....5..329M. doi: 10.5194/amt-5-329-2012 .
  9. Evans, C. L.; Xie, X. S. (2008). "Coherent Anti-Stokes Raman Scattering Microscopy: Chemical Imaging for Biology and Medicine". Annual Review of Analytical Chemistry . 1: 883–909. Bibcode:2008ARAC....1..883E. doi:10.1146/annurev.anchem.1.031207.112754. PMID   20636101.
  10. W. Demtröder, Laser Spectroscopy, 3rd Ed. (Springer, 2003).
  11. Brian Orr; J. G. Haub; Y. He; R. T. White (2016). "Spectroscopic Applications of Pulsed Tunable Optical Parametric Oscillators". In F. J. Duarte (ed.). Tunable Laser Applications (3rd ed.). Boca Raton: CRC Press. pp. 17–142. ISBN   978-1-4822-6106-6.
  12. Murray, Kermit K.; Boyd, Robert K.; Eberlin, Marcos N.; Langley, G. John; Li, Liang; Naito, Yasuhide (2013). "Definitions of terms relating to mass spectrometry (IUPAC Recommendations 2013)". Pure and Applied Chemistry . 85 (7): 1. doi: 10.1351/PAC-REC-06-04-06 . ISSN   0033-4545.
  13. N. A. Sinitsyn; Y. V. Pershin (2016). "The theory of spin noise spectroscopy: a review". Reports on Progress in Physics . 79 (10): 106501. arXiv: 1603.06858 . Bibcode:2016RPPh...79j6501S. doi:10.1088/0034-4885/79/10/106501. PMID   27615689. S2CID   4393400.
  14. Solli, D. R.; Chou, J.; Jalali, B. (2008). "Amplified wavelength–time transformation for real-time spectroscopy". Nature Photonics . 2 (1): 48–51. Bibcode:2008NaPho...2...48S. doi:10.1038/nphoton.2007.253.
  15. Chou, Jason; Solli, Daniel R.; Jalali, Bahram (2008). "Real-time spectroscopy with subgigahertz resolution using amplified dispersive Fourier transformation". Applied Physics Letters . 92 (11): 111102. arXiv: 0803.1654 . Bibcode:2008ApPhL..92k1102C. doi:10.1063/1.2896652. S2CID   53056467.
  16. "Media advisory: Press Conference to Announce Major Result from Brazilian Astronomers". ESO Announcement. Retrieved 21 August 2013.
  17. Wang, Xiping; Wacker, James P. (2006). "Using NIR Spectroscopy to Predict Weathered Wood Exposure Times" (PDF). WTCE 2006 – 9th World Conference on Timber Engineering.
  18. Sher, D. (1968). "The Relativistic Doppler Effect". Journal of the Royal Astronomical Society of Canada. 62: 105. Bibcode:1968JRASC..62..105S.
  19. 1 2 3 Andrew Fraknoi; David Morrison (October 13, 2016). "OpenStax Astronomy".

Related Research Articles

Infrared spectroscopy Interaction of infrared radiation with matter

Infrared spectroscopy is the measurement of the interaction of infrared radiation with matter by absorption, emission, or reflection. It is used to study and identify chemical substances or functional groups in solid, liquid, or gaseous forms. The method or technique of infrared spectroscopy is conducted with an instrument called an infrared spectrometer which produces an infrared spectrum. An IR spectrum can be visualized in a graph of infrared light absorbance on the vertical axis vs. frequency or wavelength on the horizontal axis. Typical units of frequency used in IR spectra are reciprocal centimeters, with the symbol cm−1. Units of IR wavelength are commonly given in micrometers, symbol μm, which are related to wave numbers in a reciprocal way. A common laboratory instrument that uses this technique is a Fourier transform infrared (FTIR) spectrometer. Two-dimensional IR is also possible as discussed below.

Atomic, molecular, and optical physics (AMO) is the study of matter-matter and light-matter interactions; at the scale of one or a few atoms and energy scales around several electron volts. The three areas are closely interrelated. AMO theory includes classical, semi-classical and quantum treatments. Typically, the theory and applications of emission, absorption, scattering of electromagnetic radiation (light) from excited atoms and molecules, analysis of spectroscopy, generation of lasers and masers, and the optical properties of matter in general, fall into these categories.

Raman spectroscopy Spectroscopic technique used to observe vibrational, rotational, and other low-frequency modes in a system

Raman spectroscopy ; is a spectroscopic technique typically used to determine vibrational modes of molecules, although rotational and other low-frequency modes of systems may also be observed. Raman spectroscopy is commonly used in chemistry to provide a structural fingerprint by which molecules can be identified.

Spectral line Optical phenomenon

A spectral line is a dark or bright line in an otherwise uniform and continuous spectrum, resulting from emission or absorption of light in a narrow frequency range, compared with the nearby frequencies. Spectral lines are often used to identify atoms and molecules. These "fingerprints" can be compared to the previously collected "fingerprints" of atoms and molecules, and are thus used to identify the atomic and molecular components of stars and planets, which would otherwise be impossible.

Emission spectrum Frequencies of light emitted by atoms or chemical compounds

The emission spectrum of a chemical element or chemical compound is the spectrum of frequencies of electromagnetic radiation emitted due to an atom or molecule making a transition from a high energy state to a lower energy state. The photon energy of the emitted photon is equal to the energy difference between the two states. There are many possible electron transitions for each atom, and each transition has a specific energy difference. This collection of different transitions, leading to different radiated wavelengths, make up an emission spectrum. Each element's emission spectrum is unique. Therefore, spectroscopy can be used to identify elements in matter of unknown composition. Similarly, the emission spectra of molecules can be used in chemical analysis of substances.

Transparency and translucency Property of an object or substance to transmit light with minimal scattering

In the field of optics, transparency is the physical property of allowing light to pass through the material without appreciable scattering of light. On a macroscopic scale, the photons can be said to follow Snell's Law. Translucency allows light to pass through, but does not necessarily follow Snell's law; the photons can be scattered at either of the two interfaces, or internally, where there is a change in index of refraction. In other words, a translucent material is made up of components with different indices of refraction. A transparent material is made up of components with a uniform index of refraction. Transparent materials appear clear, with the overall appearance of one color, or any combination leading up to a brilliant spectrum of every color. The opposite property of translucency is opacity.

Absorption spectroscopy Spectroscopic techniques that measure the absorption of radiation

Absorption spectroscopy refers to spectroscopic techniques that measure the absorption of radiation, as a function of frequency or wavelength, due to its interaction with a sample. The sample absorbs energy, i.e., photons, from the radiating field. The intensity of the absorption varies as a function of frequency, and this variation is the absorption spectrum. Absorption spectroscopy is performed across the electromagnetic spectrum.

Fluorescence spectroscopy

Fluorescence spectroscopy is a type of electromagnetic spectroscopy that analyzes fluorescence from a sample. It involves using a beam of light, usually ultraviolet light, that excites the electrons in molecules of certain compounds and causes them to emit light; typically, but not necessarily, visible light. A complementary technique is absorption spectroscopy. In the special case of single molecule fluorescence spectroscopy, intensity fluctuations from the emitted light are measured from either single fluorophores, or pairs of fluorophores.

In physics and physical chemistry, time-resolved spectroscopy is the study of dynamic processes in materials or chemical compounds by means of spectroscopic techniques. Most often, processes are studied after the illumination of a material occurs, but in principle, the technique can be applied to any process that leads to a change in properties of a material. With the help of pulsed lasers, it is possible to study processes that occur on time scales as short as 10−16 seconds.

Raman scattering

Raman scattering or the Raman effect is the inelastic scattering of photons by matter, meaning that there is both an exchange of energy and a change in the light's direction. Typically this effect involves vibrational energy being gained by a molecule as incident photons from a visible laser are shifted to lower energy. This is called normal Stokes Raman scattering. The effect is exploited by chemists and physicists to gain information about materials for a variety of purposes by performing various forms of Raman spectroscopy. Many other variants of Raman spectroscopy allow rotational energy to be examined and electronic energy levels may be examined if an X-ray source is used in addition to other possibilities. More complex techniques involving pulsed lasers, multiple laser beams and so on are known.

Resonance Raman spectroscopy is a Raman spectroscopy technique in which the incident photon energy is close in energy to an electronic transition of a compound or material under examination. The frequency coincidence can lead to greatly enhanced intensity of the Raman scattering, which facilitates the study of chemical compounds present at low concentrations.

Absorption band Range on the electromagnetic spectrum which are characteristic of a certain transition from initial to final state in a substance

According to quantum mechanics, atoms and molecules can only hold certain defined quantities of energy, or exist in specific states. When such quanta of electromagnetic radiation are emitted or absorbed by an atom or molecule, energy of the radiation changes the state of the atom or molecule from an initial state to a final state. An absorption band is a range of wavelengths, frequencies or energies in the electromagnetic spectrum which are characteristic of a particular transition from initial to final state in a substance.

Einstein coefficients

Einstein coefficients are mathematical quantities which are a measure of the probability of absorption or emission of light by an atom or molecule. The Einstein A coefficients are related to the rate of spontaneous emission of light, and the Einstein B coefficients are related to the absorption and stimulated emission of light.

Ultrafast laser spectroscopy is a spectroscopic technique that uses ultrashort pulse lasers for the study of dynamics on extremely short time scales. Different methods are used to examine the dynamics of charge carriers, atoms, and molecules. Many different procedures have been developed spanning different time scales and photon energy ranges; some common methods are listed below.

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.

Chemical imaging is the analytical capability to create a visual image of components distribution from simultaneous measurement of spectra and spatial, time information. Hyperspectral imaging measures contiguous spectral bands, as opposed to multispectral imaging which measures spaced spectral bands.

Photoelectrochemical processes are processes in photoelectrochemistry; they usually involve transforming light into other forms of energy. These processes apply to photochemistry, optically pumped lasers, sensitized solar cells, luminescence, and photochromism.

History of spectroscopy

Modern spectroscopy in the Western world started 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, which now bear his name although several of them were observed earlier by Wollaston.

Spectral line shape describes the form of a feature, observed in spectroscopy, corresponding to an energy change in an atom, molecule or ion. This shape is also referred to as the spectral line profile. Ideal line shapes include Lorentzian, Gaussian and Voigt functions, whose parameters are the line position, maximum height and half-width. Actual line shapes are determined principally by Doppler, collision and proximity broadening. For each system the half-width of the shape function varies with temperature, pressure and phase. A knowledge of shape function is needed for spectroscopic curve fitting and deconvolution.

Spectroelectrochemistry

Spectroelectrochemistry (SEC) is a set of multi-response analytical techniques in which complementary chemical information is obtained in a single experiment. Spectroelectrochemistry provides a whole vision of the phenomena that take place in the electrode process. The first spectroelectrochemical experiment was carried out by Theodore Kuwana in 1964.

References