Photosensitizer

From Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/Photosensitizer 

 

A photosensitizer being used in photodynamic therapy.

Photosensitizers produce a physicochemical change in a neighboring molecule by either donating an electron to the substrate or by abstracting a hydrogen atom from the substrate. At the end of this process, the photosensitizer eventually returns to its ground state, where it remains chemically intact until the photosensitizer absorbs more light. This means that the photosensitizer remains unchanged before and after the energetic exchange, much like heterogeneous photocatalysis. One branch of chemistry which frequently utilizes photosensitizers is polymer chemistry, using photosensitizers in reactions such as photopolymerization, photocrosslinking, and photodegradation. Photosensitizers are also used to generate prolonged excited electronic states in organic molecules with uses in photocatalysis, photon upconversion and photodynamic therapy. Generally, photosensitizers absorb electromagnetic radiation consisting of infrared radiation, visible light radiation, and ultraviolet radiation and transfer absorbed energy into neighboring molecules. This absorption of light is made possible by photosensitizers' large de-localized π-systems, which lowers the energy of HOMO and LUMO orbitals to promote photoexcitation. While many photosensitizers are organic or organometallic compounds, there are also examples of using semiconductor quantum dots as photosensitizers.

Theory

Basic schematic for all photosensitizers (PS) wherein the photosensitizer absorbs light (hν) and transfers energy to create a physicochemical change

Definition

Photosensitizers are molecules which absorb light (hν) and transfer the energy from the incident light into another nearby molecule. This light is often within the visible spectrum or infrared spectrum, as any higher energy electromagnetic radiation may result in the photoelectric effect. Upon absorbing photons of radiation from incident light, photosensitizers are able to promote a ground state electron into an excited singlet state. This electron in the excited singlet state then flips in its intrinsic spin state via Intersystem crossing to become an excited triplet state electron. The electron's lifetime in the excited state is prolonged by spin flipping in the triplet state. Prolonged triplet states provide photosensitizer molecules with an increased probability of interacting with other molecules nearby. Photosensitizers experience varying levels of efficiency for intersystem crossing at different wavelengths of light based on the internal electronic structure of the molecule.

Parameters

For a molecule to be considered a photosensitizer:

• The photosensitizer must impart a physicochemical change upon a substrate after absorbing incident light.
• Upon imparting a chemical change, the photosensitizer returns to its original chemical form.

It is important to differentiate photosensitizers from other photochemical interactions including, but not limited to, photoinitiators, photocatalysts, photoacids and photopolymerization. Photosensitizers utilize light to enact a chemical change in a substrate; after the chemical change, the photosensitizer returns to its initial state, remaining chemically unchanged from the process. Photoinitiators absorb light to become a reactive species, commonly a radical or an ion, where it then reacts with another chemical species. These photoinitiators are often completely chemically changed after their reaction. Photocatalysts accelerate chemical reactions which rely upon light. While some photosensitizers may act as photocatalysts, not all photocatalysts may act as photosensitizers. Photoacids (or photobases) are molecules which become more acidic (or basic) upon the absorption of light. Photoacids increase in acidity upon absorbing light and thermally reassociate back into their original form upon relaxing. Photoacid generators undergo an irreversible change to become an acidic species upon light absorption. Photopolymerization can occur in two ways. Photopolymerization can occur directly wherein the monomers absorb the incident light and begin polymerizing, or it can occur through a photosensitizer-mediated process where the photosensitizer absorbs the light first before transferring energy into the monomer species.

History

Photosensitizers have existed within natural systems for as long as chlorophyll and other light sensitive molecules have been a part of plant life, but studies of photosensitizers began as early as the 1900s, where scientists observed photosensitization in biological substrates and in the treatment of cancer. Mechanistic studies related to photosensitizers began with scientists analyzing the results of chemical reactions where photosensitizers photo-oxidized molecular oxygen into peroxide species. The results were understood by calculating quantum efficiencies and fluorescent yields at varying wavelengths of light and comparing these results with the yield of reactive oxygen species. However, it was not until the 1960s that the electron donating mechanism was confirmed through various spectroscopic methods including reaction-intermediate studies and luminescence studies.

The term photosensitizer does not appear in scientific literature until the 1960s. Instead, scientists would refer to photosensitizers as sensitizers used in photo-oxidation or photo-oxygenation processes. Studies during this time period involving photosensitizers utilized organic photosensitizers, consisting of aromatic hydrocarbon molecules, which could facilitate synthetic chemistry reactions. However, by the 1970s and 1980s, photosensitizers gained attraction in the scientific community for their role within biologic processes and enzymatic processes. Currently, photosensitizers are studied for their contributions to fields such as energy harvesting, photoredox catalysis in synthetic chemistry, and cancer treatment.

Diagram of a Type I photosensitized reaction

Types of photosensitization processes

There are two main pathways for photosensitized reactions.

Type I

In Type I photosensitized reactions, the photosensitizer is excited by a light source into a triplet state. The excited, triplet state photosensitizer then reacts with a substrate molecule which is not molecular oxygen to both form a product and reform the photosensitizer. Type I photosensitized reactions result in the photosensitizer being quenched by a different chemical substrate than molecular oxygen.

Diagram of a Type II photosensitized reaction

Type II

In Type II photosensitized reactions, the photosensitizer is excited by a light source into a triplet state. The excited photosensitizer then reacts with a ground state, triplet oxygen molecule. This excites the oxygen molecule into the singlet state, making it a reactive oxygen species. Upon excitation, the singlet oxygen molecule reacts with a substrate to form a product. Type II photosensitized reaction result in the photosensitizer being quenched by a ground state oxygen molecule which then goes on to react with a substrate to form a product.

Composition of photosensitizers

Photosensitizers can be placed into 3 generalized domains based on their molecular structure. These three domains are organometallic photosensitizers, organic photosensitizers, and nanomaterial photosensitizers.

Pictured are Chlorophyll A (A) and Tris(2-phenylpyridine)iridium (B), two examples of organometallic photosensitizers.

Organometallic

Pictured from top to bottom, (A) benzophenone, (B) methylene blue, and (C) rose Bengal are all organic photosensitizers. All metals involved are purely counterions to keep the material in the solid state as a salt.

Organometallic photosensitizers contain a metal atom chelated to at least one organic ligand. The photosensitizing capacities of these molecules result from electronic interactions between the metal and ligand(s). Popular electron-rich metal centers for these complexes include Iridium, Ruthenium, and Rhodium. These metals, as well as others, are common metal centers for photosensitizers due to their highly filled d-orbitals, or high d-electron counts, to promote metal to ligand charge transfer from pi-electron accepting ligands. This interaction between the metal center and the ligand leads to a large continuum of orbitals within both the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) which allows for excited electrons to switch multiplicities via intersystem crossing.  

While many organometallic photosensitizer compounds are made synthetically, there also exists naturally occurring, light-harvesting organometallic photosensitizers as well. Some relevant naturally occurring examples of organometallic photosensitizers include Chlorophyll A and Chlorophyll B.

Organic

Organic photosensitizers are carbon-based molecules which are capable of photosensitizing. The earliest studied photosensitizers were aromatic hydrocarbons which absorbed light in the presence of oxygen to produce reactive oxygen species. These organic photosensitizers are made up of highly conjugated systems which promote electron delocalization. Due to their high conjugation, these systems have a smaller gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) as well as a continuum of orbitals within the HOMO and LUMO. The smaller band gap and the continuum of orbitals in both the conduction band and the valence band allow for these materials to enter their triplet state more efficiently, making them better photosensitizers. Some notable organic photosensitizers which have been studied extensively include benzophenones, methylene blue, and rose Bengal.

Nanomaterials

Quantum dots

Colloidal quantum dots are nanoscale semiconductor materials with highly tunable optical and electronic properties. Quantum dots photosensitize via the same mechanism as organometallic photosensitizers and organic photosensitizers, but their nanoscale properties allow for greater control in distinctive aspects. Some key advantages to the use of quantum dots as photosensitizers includes their small, tunable band gap which allows for efficient transitions to the triplet state, and their insolubility in many solvents which allows for easy retrieval from a synthetic reaction mixture.

Nanorods

Nanorods, similar in size to quantum dots, have tunable optical and electronic properties. Based on their size and material composition, it is possible to tune the maximum absorption peak for nanorods during their synthesis. This control has led to the creation of photosensitizing nanorods.

Applications

Medical

Photodynamic therapy

Main article: Photodynamic therapy § Photosensitizers

Photodynamic therapy utilizes Type II photosensitizers to harvest light to degrade tumors or cancerous masses. This discovery was first observed back in 1907 by Hermann von Tappeiner when he utilized eosin to treat skin tumors. The photodynamic process is predominantly a noninvasive technique wherein the photosensitizers are put inside a patient so that it may accumulate on the tumor or cancer. When the photosensitizer reaches the tumor or cancer, wavelength specific light is shined on the outside of the patient's affected area. This light (preferably near infrared frequency as this allows for the penetration of the skin without acute toxicity) excites the photosensitizer's electrons into the triplet state. Upon excitation, the photosensitizer begins transferring energy to neighboring ground state triplet oxygen to generate excited singlet oxygen. The resulting excited oxygen species then selectively degrades the tumor or cancerous mass.

In February 2019, medical scientists announced that iridium attached to albumin, creating a photosensitized molecule, can penetrate cancer cells and, after being irradiated with light (a process called photodynamic therapy), destroy the cancer cells.

Dye sensitized solar cells are photosensitizers which transfer energy to semiconductors to generate energy from solar light

Energy sources

Dye sensitized solar cells

In 1972, scientists discovered that chlorophyll could absorb sunlight and transfer energy into electrochemical cells. This discovery eventually led to the use of photosensitizers as sunlight-harvesting materials in solar cells, mainly through the use of photosensitizer dyes. Dye Sensitized Solar cells utilize these photosensitizer dyes to absorb photons from solar light and transfer energy rich electrons to the neighboring semiconductor material to generate electric energy output. These dyes act as dopants to semiconductor surfaces which allows for the transfer of light energy from the photosensitizer to electronic energy within the semiconductor. These photosensitizers are not limited to dyes. They may take the form of any photosensitizing structure, dependent on the semiconductor material to which they are attached.

Hydrogen generating catalysts

Via the absorption of light, photosensitizers can utilize triplet state transfer to reduce small molecules, such as water, to generate Hydrogen gas. As of right now, photosensitizers have generated hydrogen gas by splitting water molecules at a small, laboratory scale.

Synthetic chemistry

Photoredox chemistry

In the early 20th century, chemists observed that various aromatic hydrocarbons in the presence of oxygen could absorb wavelength specific light to generate a peroxide species. This discovery of oxygen's reduction by a photosensitizer led to chemists studying photosensitizers as photoredox catalysts for their roles in the catalysis of pericyclic reactions and other reduction and oxidation reactions. Photosensitizers in synthetic chemistry allow for the manipulation of electronic transitions within molecules through an externally applied light source. These photosensitizers used in redox chemistry may be organic, organometallic, or nanomaterials depending on the physical and spectral properties required for the reaction.

Electromagnetic spectrum

From Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/Electromagnetic_spectrum 

Class				Wave- length ${\displaystyle \lambda }$	Freq- uency ${\displaystyle f}$	Energy per photon ${\displaystyle E}$
Ionizing radiation	γ	Gamma rays		1 pm	300 EHz	1.24 MeV
				10 pm	30 EHz	124 keV
	HX	Hard X-rays
				100 pm	3 EHz	12.4 keV
	SX	Soft X-rays
				1 nm	300 PHz	1.24 keV
				10 nm	30 PHz	124 eV
	EUV	Extreme ultraviolet
				100 nm	3 PHz	12.4 eV
	NUV	Near ultraviolet, visible
				1 μm	300 THz	1.24 eV
	NIR	Near infrared
				10 μm	30 THz	124 meV
	MIR	Mid infrared
				100 μm	3 THz	12.4 meV
	FIR	Far infrared
				1 mm	300 GHz	1.24 meV
Micro- waves and radio waves	EHF	Extremely high frequency
				1 cm	30 GHz	124 μeV
	SHF	Super high frequency
				1 dm	3 GHz	12.4 μeV
	UHF	Ultra high frequency
				1 m	300 MHz	1.24 μeV
	VHF	Very high frequency
				10 m	30 MHz	124 neV
	HF	High frequency
				100 m	3 MHz	12.4 neV
	MF	Medium frequency
				1 km	300 kHz	1.24 neV
	LF	Low frequency
				10 km	30 kHz	124 peV
	VLF	Very low frequency
				100 km	3 kHz	12.4 peV
	ULF	Ultra low frequency
				1 Mm	300 Hz	1.24 peV
	SLF	Super low frequency
				10 Mm	30 Hz	124 feV
	ELF	Extremely low frequency
				100 Mm	3 Hz	12.4 feV
Sources: File:Light spectrum.svg

The electromagnetic spectrum is the range of frequencies (the spectrum) of electromagnetic radiation and their respective wavelengths and photon energies.

The electromagnetic spectrum covers electromagnetic waves with frequencies ranging from below one hertz to above 10²⁵ hertz, corresponding to wavelengths from thousands of kilometers down to a fraction of the size of an atomic nucleus. This frequency range is divided into separate bands, and the electromagnetic waves within each frequency band are called by different names; beginning at the low frequency (long wavelength) end of the spectrum these are: radio waves, microwaves, infrared, visible light, ultraviolet, X-rays, and gamma rays at the high-frequency (short wavelength) end. The electromagnetic waves in each of these bands have different characteristics, such as how they are produced, how they interact with matter, and their practical applications. There is no known limit for long wavelengths, while it is thought that the short wavelength limit is in the vicinity of the Planck length. Extreme ultraviolet, soft X-rays, hard X-rays and gamma rays are classified as ionizing radiation as their photons have enough energy to ionize atoms, causing chemical reactions.

In most of the frequency bands above, a technique called spectroscopy can be used to physically separate waves of different frequencies, producing a spectrum showing the constituent frequencies. Spectroscopy is used to study the interactions of electromagnetic waves with matter. Other technological uses are described under electromagnetic radiation.

History and discovery

See also: History of electromagnetism, History of radio, History of electrical engineering, and History of optics

Humans have always been aware of visible light and radiant heat but for most of history it was not known that these phenomena were connected or were representatives of a more extensive principle. The ancient Greeks recognized that light traveled in straight lines and studied some of its properties, including reflection and refraction. Light was intensively studied from the beginning of the 17th century leading to the invention of important instruments like the telescope and microscope. Isaac Newton was the first to use the term spectrum for the range of colours that white light could be split into with a prism. Starting in 1666, Newton showed that these colours were intrinsic to light and could be recombined into white light. A debate arose over whether light had a wave nature or a particle nature with René Descartes, Robert Hooke and Christiaan Huygens favouring a wave description and Newton favouring a particle description. Huygens in particular had a well developed theory from which he was able to derive the laws of reflection and refraction. Around 1801, Thomas Young measured the wavelength of a light beam with his two-slit experiment thus conclusively demonstrating that light was a wave.

In 1800, William Herschel discovered infrared radiation. He was studying the temperature of different colors by moving a thermometer through light split by a prism. He noticed that the highest temperature was beyond red. He theorized that this temperature change was due to "calorific rays", a type of light ray that could not be seen. The next year, Johann Ritter, working at the other end of the spectrum, noticed what he called "chemical rays" (invisible light rays that induced certain chemical reactions). These behaved similarly to visible violet light rays, but were beyond them in the spectrum. They were later renamed ultraviolet radiation.

The study of electromagnetism began in 1820 when Hans Christian Ørsted discovered that electric currents produce magnetic fields (Oersted's law). Light was first linked to electromagnetism in 1845, when Michael Faraday noticed that the polarization of light traveling through a transparent material responded to a magnetic field (see Faraday effect). During the 1860s, James Clerk Maxwell developed four partial differential equations (Maxwell's equations) for the electromagnetic field. Two of these equations predicted the possibility and behavior of waves in the field. Analyzing the speed of these theoretical waves, Maxwell realized that they must travel at a speed that was about the known speed of light. This startling coincidence in value led Maxwell to make the inference that light itself is a type of electromagnetic wave. Maxwell's equations predicted an infinite range of frequencies of electromagnetic waves, all traveling at the speed of light. This was the first indication of the existence of the entire electromagnetic spectrum.

Maxwell's predicted waves included waves at very low frequencies compared to infrared, which in theory might be created by oscillating charges in an ordinary electrical circuit of a certain type. Attempting to prove Maxwell's equations and detect such low frequency electromagnetic radiation, in 1886, the physicist Heinrich Hertz built an apparatus to generate and detect what are now called radio waves. Hertz found the waves and was able to infer (by measuring their wavelength and multiplying it by their frequency) that they traveled at the speed of light. Hertz also demonstrated that the new radiation could be both reflected and refracted by various dielectric media, in the same manner as light. For example, Hertz was able to focus the waves using a lens made of tree resin. In a later experiment, Hertz similarly produced and measured the properties of microwaves. These new types of waves paved the way for inventions such as the wireless telegraph and the radio.

In 1895, Wilhelm Röntgen noticed a new type of radiation emitted during an experiment with an evacuated tube subjected to a high voltage. He called this radiation "x-rays" and found that they were able to travel through parts of the human body but were reflected or stopped by denser matter such as bones. Before long, many uses were found for this radiography.

The last portion of the electromagnetic spectrum was filled in with the discovery of gamma rays. In 1900, Paul Villard was studying the radioactive emissions of radium when he identified a new type of radiation that he at first thought consisted of particles similar to known alpha and beta particles, but with the power of being far more penetrating than either. However, in 1910, British physicist William Henry Bragg demonstrated that gamma rays are electromagnetic radiation, not particles, and in 1914, Ernest Rutherford (who had named them gamma rays in 1903 when he realized that they were fundamentally different from charged alpha and beta particles) and Edward Andrade measured their wavelengths, and found that gamma rays were similar to X-rays, but with shorter wavelengths.

The wave-particle debate was rekindled in 1901 when Max Planck discovered that light is only absorbed in discrete "quanta", now called photons, implying that light has a particle nature. This idea was made explicit by Albert Einstein in 1905, but never accepted by Planck and many other contemporaries. The modern position of science is that electromagnetic radiation has both a wave and a particle nature, the wave-particle duality. The contradictions arising from this position are still being debated by scientists and philosophers.

Range

Electromagnetic waves are typically described by any of the following three physical properties: the frequency f, wavelength λ, or photon energy E. Frequencies observed in astronomy range from 2.4×10²³ Hz (1 GeV gamma rays) down to the local plasma frequency of the ionized interstellar medium (~1 kHz). Wavelength is inversely proportional to the wave frequency, so gamma rays have very short wavelengths that are fractions of the size of atoms, whereas wavelengths on the opposite end of the spectrum can be indefinitely long. Photon energy is directly proportional to the wave frequency, so gamma ray photons have the highest energy (around a billion electron volts), while radio wave photons have very low energy (around a femtoelectronvolt). These relations are illustrated by the following equations:

${\displaystyle f={\frac {c}{\lambda }},\quad {\text{or}}\quad f={\frac {E}{h}},\quad {\text{or}}\quad E={\frac {hc}{\lambda }},}$

where:

• c = 299792458 m/s is the speed of light in a vacuum
• h = 6.62607015×10⁻³⁴ J·s = 4.13566733(10)×10⁻¹⁵ eV·s is Planck's constant.

Whenever electromagnetic waves exist in a medium with matter, their wavelength is decreased. Wavelengths of electromagnetic radiation, whatever medium they are traveling through, are usually quoted in terms of the vacuum wavelength, although this is not always explicitly stated.

Generally, electromagnetic radiation is classified by wavelength into radio wave, microwave, infrared, visible light, ultraviolet, X-rays and gamma rays. The behavior of EM radiation depends on its wavelength. When EM radiation interacts with single atoms and molecules, its behavior also depends on the amount of energy per quantum (photon) it carries.

Spectroscopy can detect a much wider region of the EM spectrum than the visible wavelength range of 400 nm to 700 nm in a vacuum. A common laboratory spectroscope can detect wavelengths from 2 nm to 2500 nm. Detailed information about the physical properties of objects, gases, or even stars can be obtained from this type of device. Spectroscopes are widely used in astrophysics. For example, many hydrogen atoms emit a radio wave photon that has a wavelength of 21.12 cm. Also, frequencies of 30 Hz and below can be produced by and are important in the study of certain stellar nebulae and frequencies as high as 2.9×10²⁷ Hz have been detected from astrophysical sources.

Regions

 

The electromagnetic spectrum

A diagram of the electromagnetic spectrum, showing various properties across the range of frequencies and wavelengths

The types of electromagnetic radiation are broadly classified into the following classes (regions, bands or types):

1. Gamma radiation
2. X-ray radiation
3. Ultraviolet radiation
4. Visible light
5. Infrared radiation
6. Microwave radiation
7. Radio waves

This classification goes in the increasing order of wavelength, which is characteristic of the type of radiation.

There are no precisely defined boundaries between the bands of the electromagnetic spectrum; rather they fade into each other like the bands in a rainbow (which is the sub-spectrum of visible light). Radiation of each frequency and wavelength (or in each band) has a mix of properties of the two regions of the spectrum that bound it. For example, red light resembles infrared radiation in that it can excite and add energy to some chemical bonds and indeed must do so to power the chemical mechanisms responsible for photosynthesis and the working of the visual system.

The distinction between X-rays and gamma rays is partly based on sources: the photons generated from nuclear decay or other nuclear and subnuclear/particle process are always termed gamma rays, whereas X-rays are generated by electronic transitions involving highly energetic inner atomic electrons. In general, nuclear transitions are much more energetic than electronic transitions, so gamma rays are more energetic than X-rays, but exceptions exist. By analogy to electronic transitions, muonic atom transitions are also said to produce X-rays, even though their energy may exceed 6 megaelectronvolts (0.96 pJ), whereas there are many (77 known to be less than 10 keV (1.6 fJ)) low-energy nuclear transitions (e.g., the 7.6 eV (1.22 aJ) nuclear transition of thorium-229m), and, despite being one million-fold less energetic than some muonic X-rays, the emitted photons are still called gamma rays due to their nuclear origin.

The convention that EM radiation that is known to come from the nucleus is always called "gamma ray" radiation is the only convention that is universally respected, however. Many astronomical gamma ray sources (such as gamma ray bursts) are known to be too energetic (in both intensity and wavelength) to be of nuclear origin. Quite often, in high-energy physics and in medical radiotherapy, very high energy EMR (in the > 10 MeV region)—which is of higher energy than any nuclear gamma ray—is not called X-ray or gamma ray, but instead by the generic term of "high-energy photons".

The region of the spectrum where a particular observed electromagnetic radiation falls is reference frame-dependent (due to the Doppler shift for light), so EM radiation that one observer would say is in one region of the spectrum could appear to an observer moving at a substantial fraction of the speed of light with respect to the first to be in another part of the spectrum. For example, consider the cosmic microwave background. It was produced when matter and radiation decoupled, by the de-excitation of hydrogen atoms to the ground state. These photons were from Lyman series transitions, putting them in the ultraviolet (UV) part of the electromagnetic spectrum. Now this radiation has undergone enough cosmological red shift to put it into the microwave region of the spectrum for observers moving slowly (compared to the speed of light) with respect to the cosmos.

Rationale for names

Electromagnetic radiation interacts with matter in different ways across the spectrum. These types of interaction are so different that historically different names have been applied to different parts of the spectrum, as though these were different types of radiation. Thus, although these "different kinds" of electromagnetic radiation form a quantitatively continuous spectrum of frequencies and wavelengths, the spectrum remains divided for practical reasons related to these qualitative interaction differences.

Electromagnetic radiation interaction with matter

Region of the spectrum	Main interactions with matter
Radio	Collective oscillation of charge carriers in bulk material (plasma oscillation). An example would be the oscillatory travels of the electrons in an antenna.
Microwave through far infrared	Plasma oscillation, molecular rotation
Near infrared	Molecular vibration, plasma oscillation (in metals only)
Visible	Molecular electron excitation (including pigment molecules found in the human retina), plasma oscillations (in metals only)
Ultraviolet	Excitation of molecular and atomic valence electrons, including ejection of the electrons (photoelectric effect)
X-rays	Excitation and ejection of core atomic electrons, Compton scattering (for low atomic numbers)
Gamma rays	Energetic ejection of core electrons in heavy elements, Compton scattering (for all atomic numbers), excitation of atomic nuclei, including dissociation of nuclei
High-energy gamma rays	Creation of particle-antiparticle pairs. At very high energies a single photon can create a shower of high-energy particles and antiparticles upon interaction with matter.

Types of radiation

Radio waves

Main articles: Radio frequency, Radio spectrum, and Radio waves

Radio waves are emitted and received by antennas, which consist of conductors such as metal rod resonators. In artificial generation of radio waves, an electronic device called a transmitter generates an AC electric current which is applied to an antenna. The oscillating electrons in the antenna generate oscillating electric and magnetic fields that radiate away from the antenna as radio waves. In reception of radio waves, the oscillating electric and magnetic fields of a radio wave couple to the electrons in an antenna, pushing them back and forth, creating oscillating currents which are applied to a radio receiver. Earth's atmosphere is mainly transparent to radio waves, except for layers of charged particles in the ionosphere which can reflect certain frequencies.

Radio waves are extremely widely used to transmit information across distances in radio communication systems such as radio broadcasting, television, two way radios, mobile phones, communication satellites, and wireless networking. In a radio communication system, a radio frequency current is modulated with an information-bearing signal in a transmitter by varying either the amplitude, frequency or phase, and applied to an antenna. The radio waves carry the information across space to a receiver, where they are received by an antenna and the information extracted by demodulation in the receiver. Radio waves are also used for navigation in systems like Global Positioning System (GPS) and navigational beacons, and locating distant objects in radiolocation and radar. They are also used for remote control, and for industrial heating.

The use of the radio spectrum is strictly regulated by governments, coordinated by the International Telecommunication Union (ITU) which allocates frequencies to different users for different uses.

Microwaves

Main article: Microwaves

 

Plot of Earth's atmospheric opacity to various wavelengths of electromagnetic radiation. This is the surface-to-space opacity, the atmosphere is transparent to longwave radio transmissions within the troposphere but opaque to space due to the ionosphere.

 

Plot of atmospheric opacity for terrestial to terrestial transmission showing the molecules responsible for some of the resonances

Microwaves are radio waves of short wavelength, from about 10 centimeters to one millimeter, in the SHF and EHF frequency bands. Microwave energy is produced with klystron and magnetron tubes, and with solid state devices such as Gunn and IMPATT diodes. Although they are emitted and absorbed by short antennas, they are also absorbed by polar molecules, coupling to vibrational and rotational modes, resulting in bulk heating. Unlike higher frequency waves such as infrared and light which are absorbed mainly at surfaces, microwaves can penetrate into materials and deposit their energy below the surface. This effect is used to heat food in microwave ovens, and for industrial heating and medical diathermy. Microwaves are the main wavelengths used in radar, and are used for satellite communication, and wireless networking technologies such as Wi-Fi. The copper cables (transmission lines) which are used to carry lower frequency radio waves to antennas have excessive power losses at microwave frequencies, and metal pipes called waveguides are used to carry them. Although at the low end of the band the atmosphere is mainly transparent, at the upper end of the band absorption of microwaves by atmospheric gasses limits practical propagation distances to a few kilometers.

Terahertz radiation or sub-millimeter radiation is a region of the spectrum from about 100 GHz to 30 terahertz (THz) between microwaves and far infrared which can be regarded as belonging to either band. Until recently, the range was rarely studied and few sources existed for microwave energy in the so-called terahertz gap, but applications such as imaging and communications are now appearing. Scientists are also looking to apply terahertz technology in the armed forces, where high-frequency waves might be directed at enemy troops to incapacitate their electronic equipment. Terahertz radiation is strongly absorbed by atmospheric gases, making this frequency range useless for long-distance communication.

Infrared radiation

Main article: Infrared radiation

The infrared part of the electromagnetic spectrum covers the range from roughly 300 GHz to 400 THz (1 mm – 750 nm). It can be divided into three parts:

• Far-infrared, from 300 GHz to 30 THz (1 mm – 10 μm). The lower part of this range may also be called microwaves or terahertz waves. This radiation is typically absorbed by so-called rotational modes in gas-phase molecules, by molecular motions in liquids, and by phonons in solids. The water in Earth's atmosphere absorbs so strongly in this range that it renders the atmosphere in effect opaque. However, there are certain wavelength ranges ("windows") within the opaque range that allow partial transmission, and can be used for astronomy. The wavelength range from approximately 200 μm up to a few mm is often referred to as Submillimetre astronomy, reserving far infrared for wavelengths below 200 μm.
• Mid-infrared, from 30 to 120 THz (10–2.5 μm). Hot objects (black-body radiators) can radiate strongly in this range, and human skin at normal body temperature radiates strongly at the lower end of this region. This radiation is absorbed by molecular vibrations, where the different atoms in a molecule vibrate around their equilibrium positions. This range is sometimes called the fingerprint region, since the mid-infrared absorption spectrum of a compound is very specific for that compound.
• Near-infrared, from 120 to 400 THz (2,500–750 nm). Physical processes that are relevant for this range are similar to those for visible light. The highest frequencies in this region can be detected directly by some types of photographic film, and by many types of solid state image sensors for infrared photography and videography.

Visible light

Color	Wavelength (nm)	Frequency (THz)	Photon energy (eV)
violet	380–450	670–790	2.75–3.26
blue	450–485	620–670	2.56–2.75
cyan	485–500	600–620	2.48–2.56
green	500–565	530–600	2.19–2.48
yellow	565–590	510–530	2.10–2.19
orange	590–625	480–510	1.98–2.10
red	625–750	400–480	1.65–1.98

 

Main article: Visible spectrum

Above infrared in frequency comes visible light. The Sun emits its peak power in the visible region, although integrating the entire emission power spectrum through all wavelengths shows that the Sun emits slightly more infrared than visible light. By definition, visible light is the part of the EM spectrum the human eye is the most sensitive to. Visible light (and near-infrared light) is typically absorbed and emitted by electrons in molecules and atoms that move from one energy level to another. This action allows the chemical mechanisms that underlie human vision and plant photosynthesis. The light that excites the human visual system is a very small portion of the electromagnetic spectrum. A rainbow shows the optical (visible) part of the electromagnetic spectrum; infrared (if it could be seen) would be located just beyond the red side of the rainbow whilst ultraviolet would appear just beyond the opposite violet end.

Electromagnetic radiation with a wavelength between 380 nm and 760 nm (400–790 terahertz) is detected by the human eye and perceived as visible light. Other wavelengths, especially near infrared (longer than 760 nm) and ultraviolet (shorter than 380 nm) are also sometimes referred to as light, especially when the visibility to humans is not relevant. White light is a combination of lights of different wavelengths in the visible spectrum. Passing white light through a prism splits it up into the several colors of light observed in the visible spectrum between 400 nm and 780 nm.

If radiation having a frequency in the visible region of the EM spectrum reflects off an object, say, a bowl of fruit, and then strikes the eyes, this results in visual perception of the scene. The brain's visual system processes the multitude of reflected frequencies into different shades and hues, and through this insufficiently-understood psychophysical phenomenon, most people perceive a bowl of fruit.

At most wavelengths, however, the information carried by electromagnetic radiation is not directly detected by human senses. Natural sources produce EM radiation across the spectrum, and technology can also manipulate a broad range of wavelengths. Optical fiber transmits light that, although not necessarily in the visible part of the spectrum (it is usually infrared), can carry information. The modulation is similar to that used with radio waves.

Ultraviolet radiation

Main article: Ultraviolet

 

The amount of penetration of UV relative to altitude in Earth's ozone

Next in frequency comes ultraviolet (UV). The wavelength of UV rays is shorter than the violet end of the visible spectrum but longer than the X-ray.

UV is the longest wavelength radiation whose photons are energetic enough to ionize atoms, separating electrons from them, and thus causing chemical reactions. Short wavelength UV and the shorter wavelength radiation above it (X-rays and gamma rays) are called ionizing radiation, and exposure to them can damage living tissue, making them a health hazard. UV can also cause many substances to glow with visible light; this is called fluorescence.

At the middle range of UV, UV rays cannot ionize but can break chemical bonds, making molecules unusually reactive. Sunburn, for example, is caused by the disruptive effects of middle range UV radiation on skin cells, which is the main cause of skin cancer. UV rays in the middle range can irreparably damage the complex DNA molecules in the cells producing thymine dimers making it a very potent mutagen.

The Sun emits significant UV radiation (about 10% of its total power), including extremely short wavelength UV that could potentially destroy most life on land (ocean water would provide some protection for life there). However, most of the Sun's damaging UV wavelengths are absorbed by the atmosphere before they reach the surface. The higher energy (shortest wavelength) ranges of UV (called "vacuum UV") are absorbed by nitrogen and, at longer wavelengths, by simple diatomic oxygen in the air. Most of the UV in the mid-range of energy is blocked by the ozone layer, which absorbs strongly in the important 200–315 nm range, the lower energy part of which is too long for ordinary dioxygen in air to absorb. This leaves less than 3% of sunlight at sea level in UV, with all of this remainder at the lower energies. The remainder is UV-A, along with some UV-B. The very lowest energy range of UV between 315 nm and visible light (called UV-A) is not blocked well by the atmosphere, but does not cause sunburn and does less biological damage. However, it is not harmless and does create oxygen radicals, mutations and skin damage.

X-rays

Main article: X-rays

After UV come X-rays, which, like the upper ranges of UV are also ionizing. However, due to their higher energies, X-rays can also interact with matter by means of the Compton effect. Hard X-rays have shorter wavelengths than soft X-rays and as they can pass through many substances with little absorption, they can be used to 'see through' objects with 'thicknesses' less than that equivalent to a few meters of water. One notable use is diagnostic X-ray imaging in medicine (a process known as radiography). X-rays are useful as probes in high-energy physics. In astronomy, the accretion disks around neutron stars and black holes emit X-rays, enabling studies of these phenomena. X-rays are also emitted by stellar corona and are strongly emitted by some types of nebulae. However, X-ray telescopes must be placed outside the Earth's atmosphere to see astronomical X-rays, since the great depth of the atmosphere of Earth is opaque to X-rays (with areal density of 1000 g/cm²), equivalent to 10 meters thickness of water. This is an amount sufficient to block almost all astronomical X-rays (and also astronomical gamma rays—see below).

Gamma rays

Main article: Gamma rays

After hard X-rays come gamma rays, which were discovered by Paul Ulrich Villard in 1900. These are the most energetic photons, having no defined lower limit to their wavelength. In astronomy they are valuable for studying high-energy objects or regions, however as with X-rays this can only be done with telescopes outside the Earth's atmosphere. Gamma rays are used experimentally by physicists for their penetrating ability and are produced by a number of radioisotopes. They are used for irradiation of foods and seeds for sterilization, and in medicine they are occasionally used in radiation cancer therapy. More commonly, gamma rays are used for diagnostic imaging in nuclear medicine, an example being PET scans. The wavelength of gamma rays can be measured with high accuracy through the effects of Compton scattering.