Spectroscopy


Spectroscopy is the field of study that measures and interprets electromagnetic spectra as it interacts with matter. In narrower contexts, spectroscopy is the precise study of color as generalized from radiated visible light to all bands of the electromagnetic spectrum.
Spectroscopy, primarily in the electromagnetic spectrum, is a fundamental exploratory tool in the fields of astronomy, chemistry, materials science, and physics, allowing the composition, physical and electronic structure of matter to be investigated at the atomic, molecular and macro scale, and over astronomical distances.
Historically, spectroscopy originated as the study of the wavelength dependence of the absorption by gas phase matter of visible light dispersed by a prism. Current applications of spectroscopy include biomedical spectroscopy in the areas of tissue analysis and medical imaging. Matter waves and acoustic waves can 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.

Introduction

Spectroscopy is a branch of science concerned with the spectra of electromagnetic radiation as a function of its wavelength or frequency, as measured by spectrographic equipment and other techniques, in order to obtain information concerning the structure and properties of matter. Spectral measurement devices are referred to as spectrometers, spectrophotometers, spectrographs or spectral analyzers. Most spectroscopic analysis in the laboratory starts with a sample to be analyzed. A light source is sent through a monochromator to spatially separate the colors before passing a selected frequency band through the sample, then the output is captured by a photodiode. For astronomical purposes, the telescope must be equipped with the light dispersion device. There are various versions of this basic setup that may be employed.
Spectroscopy began with Isaac Newton splitting light with a prism; a key moment in the development of modern optics. Therefore, it was originally the study of visible light that we call color. Following the contributions of James Clerk Maxwell, this study later came to include the entire electromagnetic spectrum. Although color is involved in spectroscopy, it is not equivalent to the absorption and reflection of certain electromagnetic waves that give objects or elements a sense of color to our eyes. Rather, spectroscopy involves the splitting of light by a prism, diffraction grating, or similar instrument, to display a particular discrete line pattern called a "spectrum", which is unique for each different type of element or molecule. Most elements are first put into a gaseous state to allow the spectra to be examined, although today other methods can be used for different phases of matter. Each element that is diffracted by a prism-like instrument displays either an absorption spectrum or an emission spectrum depending upon whether the element is being cooled or heated.
Until recently all spectroscopy involved the study of line spectra and most spectroscopy still does. Vibrational spectroscopy is the branch of spectroscopy that studies the spectra. However, the latest developments in spectroscopy can sometimes dispense with the dispersion technique. In biochemical spectroscopy, information can be gathered about biological tissue by absorption and light scattering techniques. Light scattering spectroscopy is a type of reflectance spectroscopy that determines tissue structures by examining elastic scattering. In such a case, it is the tissue that acts as a diffraction or dispersion mechanism.
Spectroscopic studies were central to the development of quantum mechanics. The first useful quantum atomic models, including Bohr model, the Schrödinger equation, and Matrix mechanics, reproduced the spectral lines of hydrogen. These equated discrete quantum jumps of the bound electron in a hydrogen atom to the discrete hydrogen spectrum. Max Planck's explanation of blackbody radiation involved spectroscopy because he was comparing the wavelength of light using a photometer to the temperature of a Black Body. 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 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, elemental abundances, velocity, rotation, magnetic field, and more. An important use for spectroscopy is in biochemistry. Molecular samples may be analyzed for species identification and energy content.

Theory

The underlying premise of spectroscopy is that light is made of different wavelengths and that each wavelength corresponds to a different frequency. The importance of spectroscopy is centered around the fact that every element in the periodic table has a unique light spectrum described by the frequencies of light it emits or absorbs consistently appearing in the same part of the electromagnetic spectrum when that light is diffracted. This opened up an entire field of study with anything that contains atoms. Spectroscopy is the key to understanding the atomic properties of all matter. As such spectroscopy opened up many new sub-fields of science yet undiscovered. The idea that each atomic element has its unique spectral signature enabled spectroscopy to be used in a broad number of fields each with a specific goal achieved by different spectroscopic procedures. The National Institute of Standards and Technology maintains a public Atomic Spectra Database that is continually updated with precise measurements.
With an absorption spectrophotometer, the level of absorption of a light source is determined by the Beer-Lambert Law:
where is the light intensity before passing through the sample, is the output intensity, is the extinction coefficient, is the path length through the sample, and is the concentration of the sample. The extinction coefficient depends on the wavelength selected and the molecule being sampled.
Resonances by the frequency were first characterized in mechanical systems such as pendulums, which have a frequency of motion noted famously by Galileo. In quantum mechanical systems, the analogous resonance is a coupling of two quantum mechanical stationary states of a system, such as two atomic orbitals, via an oscillatory source of energy such as a photon. The coupling of the two states is strongest when the source energy matches the energy difference between the two states. That is, a photon at the right energy is more likely to cause an electron to jump between two orbitals, a process called electron excitation. The energy of a photon is related to its frequency by where is the Planck constant, and so a spectrum of the system response vs. photon frequency will peak at the resonant frequency or energy.
Any part of the electromagnetic spectrum may be used to analyze a sample from the infrared to the ultraviolet telling scientists different properties about the very same sample, a discovery that led to a broadening of the field of spectroscopy. For instance in chemical analysis, the most common types of spectroscopy include atomic spectroscopy, infrared spectroscopy, ultraviolet and visible spectroscopy, Raman spectroscopy and nuclear magnetic resonance. In nuclear magnetic resonance, the theory behind it is that frequency is analogous to resonance and its corresponding resonant frequency.

Classification of methods

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:
The types of spectroscopy can be distinguished by the nature of the interaction between the energy and the material. These interactions include:
  • Absorption spectroscopy: Absorption occurs when energy from the radiative source is absorbed by the material. Absorption is often determined by measuring the fraction of energy transmitted through the material, with absorption decreasing the transmitted portion.
  • Emission spectroscopy: Emission indicates that radiative energy is released by the material. A material's blackbody spectrum is a spontaneous emission spectrum determined by its temperature. This feature can be measured in the infrared by instruments such as the atmospheric emitted radiance interferometer. Emission can be induced by other sources of energy such as flames, sparks, electric arcs or electromagnetic radiation in the case of fluorescence.
  • Elastic scattering and reflection spectroscopy determine how incident radiation is reflected or scattered by a material. Crystallography employs the scattering of high energy radiation, such as X-rays and electrons, to examine the arrangement of atoms in proteins and solid crystals.
  • Impedance spectroscopy, where impedance is the ability of a medium to impede or slow the transmittance of energy. For optical applications, this is characterized by the index of refraction.
  • Inelastic scattering phenomena involve an exchange of energy between X-ray radiation and the matter that shifts the wavelength of the scattered radiation. These include Raman and Compton scattering.
  • Coherent or resonance spectroscopy are techniques where the radiative energy couples two quantum states of the material in a coherent interaction that is sustained by the radiating field. The coherence can be disrupted by other interactions, such as particle collisions and energy transfer, and so often requires high intensity radiation to be sustained. Nuclear magnetic resonance spectroscopy is a widely used resonance method, and ultrafast laser spectroscopy is possible in the infrared and visible spectral regions.
  • Nuclear spectroscopy are methods that use the properties of specific nuclei to probe the local structure in matter, mainly condensed matter, molecules in liquids or frozen liquids and bio-molecules.
  • Quantum logic spectroscopy is a general technique used in ion traps that enables precision spectroscopy of ions with internal structures that preclude laser cooling, state manipulation, and detection. Quantum logic operations enable a controllable ion to exchange information with a co-trapped ion that has a complex or unknown electronic structure.