Electrochemical processes involving photons and the emission or absorption of light
Photoelectrochemical processes are processes in photoelectrochemistry; they usually involve transforming light into other forms of energy.[1] These processes apply to photochemistry, optically pumped lasers, sensitized solar cells, luminescence, and photochromism.
After absorbing energy, an electron may jump from the ground state to a higher energy excited state.
Electron excitation is the movement of an electron to a higher energy state. This can either be done by photoexcitation (PE), where the original electron absorbs the photon and gains all the photon's energy or by electrical excitation (EE), where the original electron absorbs the energy of another, energetic electron. Within a semiconductor crystal lattice, thermal excitation is a process where lattice vibrations provide enough energy to move electrons to a higher energy band. When an excited electron falls back to a lower energy state again, it is called electron relaxation. This can be done by radiation of a photon or giving the energy to a third spectator particle as well.[2]
In physics there is a specific technical definition for energy level which is often associated with an atom being excited to an excited state. The excited state, in general, is in relation to the ground state, where the excited state is at a higher energy level than the ground state.
Photoexcitation is the mechanism of electron excitation by photon absorption, when the energy of the photon is too low to cause photoionization. The absorption of the photon takes place in accordance with Planck's quantum theory.
In chemistry, photoisomerization is molecular behavior in which structural change between isomers is caused by photoexcitation. Both reversible and irreversible photoisomerization reactions exist. However, the word "photoisomerization" usually indicates a reversible process. Photoisomerizable molecules are already put to practical use, for instance, in pigments for rewritable CDs, DVDs, and 3D optical data storage solutions. In addition, recent interest in photoisomerizable molecules has been aimed at molecular devices, such as molecular switches,[3] molecular motors,[4] and molecular electronics.
Photoisomerization behavior can be roughly categorized into several classes. Two major classes are trans-cis (or 'E-'Z) conversion, and open-closed ring transition. Examples of the former include stilbene and azobenzene. This type of compounds has a double bond, and rotation or inversion around the double bond affords isomerization between the two states. Examples of the latter include fulgide and diarylethene. This type of compounds undergoes bond cleavage and bond creation upon irradiation with particular wavelengths of light. Still another class is the di-π-methane rearrangement.
Photoionization is the physical process in which an incident photon ejects one or more electrons from an atom, ion or molecule. This is essentially the same process that occurs with the photoelectric effect with metals. In the case of a gas or single atoms, the term photoionization is more common.[5]
The ejected electrons, known as photoelectrons, carry information about their pre-ionized states. For example, a single electron can have a kinetic energy equal to the energy of the incident photon minus the electron binding energy of the state it left. Photons with energies less than the electron binding energy may be absorbed or scattered but will not photoionize the atom or ion.[5]
For example, to ionize hydrogen, photons need an energy greater than 13.6 electronvolts (the Rydberg energy), which corresponds to a wavelength of 91.2 nm.[6] For photons with greater energy than this, the energy of the emitted photoelectron is given by:
Not every photon which encounters an atom or ion will photoionize it. The probability of photoionization is related to the photoionization cross-section, which depends on the energy of the photon and the target being considered. For photon energies below the ionization threshold, the photoionization cross-section is near zero. But with the development of pulsed lasers it has become possible to create extremely intense, coherent light where multi-photon ionization may occur. At even higher intensities (around 1015 - 1016 W/cm2 of infrared or visible light), non-perturbative phenomena such as barrier suppression ionization[7] and rescattering ionization[8] are observed.
Several photons of energy below the ionization threshold may actually combine their energies to ionize an atom. This probability decreases rapidly with the number of photons required, but the development of very intense, pulsed lasers still makes it possible. In the perturbative regime (below about 1014 W/cm2 at optical frequencies), the probability of absorbing N photons depends on the laser-light intensity I as IN.[9]
Above threshold ionization (ATI) [10] is an extension of multi-photon ionization where even more photons are absorbed than actually would be necessary to ionize the atom. The excess energy gives the released electron higher kinetic energy than the usual case of just-above threshold ionization. More precisely, the system will have multiple peaks in its photoelectron spectrum which are separated by the photon energies, this indicates that the emitted electron has more kinetic energy than in the normal (lowest possible number of photons) ionization case. The electrons released from the target will have approximately an integer number of photon-energies more kinetic energy. In intensity regions between 1014 W/cm2 and 1018 W/cm2, each of MPI, ATI, and barrier suppression ionization can occur simultaneously, each contributing to the overall ionization of the atoms involved.[11]
In semiconductor physics the Photo-Dember effect (named after its discoverer H. Dember) consists in the formation of a charge dipole in the vicinity of a semiconductor surface after ultra-fast photo-generation of charge carriers. The dipole forms owing to the difference of mobilities (or diffusion constants) for holes and electrons which combined with the break of symmetry provided by the surface lead to an effective charge separation in the direction perpendicular to the surface.[12]
Grotthuss–Draper law
The Grotthuss–Draper law (also called the principle of photochemical activation) states that only that light which is absorbed by a system can bring about a photochemical change. Materials such as dyes and phosphors must be able to absorb "light" at optical frequencies. This law provides a basis for fluorescence and phosphorescence. The law was first proposed in 1817 by Theodor Grotthuss and in 1842, independently, by John William Draper.[5]
This is considered to be one of the two basic laws of photochemistry. The second law is the Stark–Einstein law, which says that primary chemical or physical reactions occur with each photon absorbed.[5]
Stark–Einstein law
The Stark–Einstein law is named after German-born physicists Johannes Stark and Albert Einstein, who independently formulated the law between 1908 and 1913. It is also known as the photochemical equivalence law or photoequivalence law. In essence it says that every photon that is absorbed will cause a (primary) chemical or physical reaction.[13]
The photon is a quantum of radiation, or one unit of radiation. Therefore, this is a single unit of EM radiation that is equal to the Planck constant (h) times the frequency of light. This quantity is symbolized by γ, hν, or ħω.
The photochemical equivalence law is also restated as follows: for every mole of a substance that reacts, an equivalent mole of quanta of light are absorbed. The formula is:[13]
The photochemical equivalence law applies to the part of a light-induced reaction that is referred to as the primary process (i.e. absorption or fluorescence).[13]
In most photochemical reactions the primary process is usually followed by so-called secondary photochemical processes that are normal interactions between reactants not requiring absorption of light. As a result, such reactions do not appear to obey the one quantum–one molecule reactant relationship.[13]
The law is further restricted to conventional photochemical processes using light sources with moderate intensities; high-intensity light sources such as those used in flash photolysis and in laser experiments are known to cause so-called biphotonic processes; i.e., the absorption by a molecule of a substance of two photons of light.[13]
In physics, absorption of electromagnetic radiation is the way by which the energy of a photon is taken up by matter, typically the electrons of an atom. Thus, the electromagnetic energy is transformed to other forms of energy, for example, to heat. The absorption of light during wave propagation is often called attenuation. Usually, the absorption of waves does not depend on their intensity (linear absorption), although in certain conditions (usually, in optics), the medium changes its transparency dependently on the intensity of waves going through, and the Saturable absorption (or nonlinear absorption) occurs.
Photosensitization
Photosensitization is a process of transferring the energy of absorbed light. After absorption, the energy is transferred to the (chosen) reactants. This is part of the work of photochemistry in general. In particular this process is commonly employed where reactions require light sources of certain wavelengths that are not readily available.[14]
For example, mercury absorbs radiation at 1849 and 2537 angstroms, and the source is often high-intensity mercury lamps. It is a commonly used sensitizer. When mercury vapor is mixed with ethylene, and the compound is irradiated with a mercury lamp, this results in the photodecomposition of ethylene to acetylene. This occurs on absorption of light to yield excited state mercury atoms, which are able to transfer this energy to the ethylene molecules, and are in turn deactivated to their initial energy state.[14]
For the particulate material used to create voids that aid in the initiation or propagation of an explosive's detonation wave, see Explosive sensitiser .
A sensitizer in chemiluminescence is a chemical compound, capable of light emission after it has received energy from a molecule, which became excited previously in the chemical reaction. A good example is this:
O2*is excited oxygen– meaning, one or more electrons in the O2 molecule have been promoted to higher-energy molecular orbitals. Hence, oxygen produced by this chemical reaction somehow 'absorbed' the energy released by the reaction and became excited. This energy state is unstable, therefore it will return to the ground state by lowering its energy. It can do that in more than one way:
it can react further, without any light emission
it can lose energy without emission, for example, giving off heat to the surroundings or transferring energy to another molecule
it can emit light
The intensity, duration and color of emitted light depend on quantum and kinetical factors. However, excited molecules are frequently less capable of light emission in terms of brightness and duration when compared to sensitizers. This is because sensitizers can store energy (that is, be excited) for longer periods of time than other excited molecules. The energy is stored through means of quantum vibration, so sensitizers are usually compounds which either include systems of aromatic rings or many conjugated double and triple bonds in their structure. Hence, if an excited molecule transfers its energy to a sensitizer thus exciting it, longer and easier to quantify light emission is often observed.
The color (that is, the wavelength), brightness and duration of emission depend upon the sensitizer used. Usually, for a certain chemical reaction, many different sensitizers can be used.
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.[15][16]
In physics, specifically statistical mechanics, a population inversion occurs while a system exists in a state in which more members of the system are in higher, excited states than in lower, unexcited energy states. It is called an "inversion" because in many familiar and commonly encountered physical systems, this is not possible. This concept is of fundamental importance in laser science because the production of a population inversion is a necessary step in the workings of a standard laser.
Stimulated emission is the process by which an incoming photon of a specific frequency can interact with an excited atomic electron, causing it to drop to a lower energy level. The liberated energy transfers to the electromagnetic field, creating a new photon with a frequency, polarization, and direction of travel that are all identical to the photons of the incident wave. This is in contrast to spontaneous emission, which occurs at a characteristic rate for each of the atoms/oscillators in the upper energy state regardless of the external electromagnetic field.
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.
Ionization is the process by which an atom or a molecule acquires a negative or positive charge by gaining or losing electrons, often in conjunction with other chemical changes. The resulting electrically charged atom or molecule is called an ion. Ionization can result from the loss of an electron after collisions with subatomic particles, collisions with other atoms, molecules, electrons, positrons, protons, antiprotons and ions, or through the interaction with electromagnetic radiation. Heterolytic bond cleavage and heterolytic substitution reactions can result in the formation of ion pairs. Ionization can occur through radioactive decay by the internal conversion process, in which an excited nucleus transfers its energy to one of the inner-shell electrons causing it to be ejected.
Photochemistry is the branch of chemistry concerned with the chemical effects of light. Generally, this term is used to describe a chemical reaction caused by absorption of ultraviolet, visible (400–750 nm), or infrared radiation (750–2500 nm).
In physics, atomic spectroscopy is the study of the electromagnetic radiation absorbed and emitted by atoms. Since unique elements have unique emission spectra, atomic spectroscopy is applied for determination of elemental compositions. It can be divided by atomization source or by the type of spectroscopy used. In the latter case, the main division is between optical and mass spectrometry. Mass spectrometry generally gives significantly better analytical performance, but is also significantly more complex. This complexity translates into higher purchase costs, higher operational costs, more operator training, and a greater number of components that can potentially fail. Because optical spectroscopy is often less expensive and has performance adequate for many tasks, it is far more common. Atomic absorption spectrometers are one of the most commonly sold and used analytical devices.
Electron excitation is the transfer of a bound electron to a more energetic, but still bound state. This can be done by photoexcitation (PE), where the electron absorbs a photon and gains all its energy or by collisional excitation (CE), where the electron receives energy from a collision with another, energetic electron. Within a semiconductor crystal lattice, thermal excitation is a process where lattice vibrations provide enough energy to transfer electrons to a higher energy band such as a more energetic sublevel or energy level. When an excited electron falls back to a state of lower energy, it undergoes electron relaxation (deexcitation). This is accompanied by the emission of a photon or by a transfer of energy to another particle. The energy released is equal to the difference in energy levels between the electron energy states.
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. All time-resolved spectra are suitable to be analyzed using the two-dimensional correlation method for a correlation map between the peaks.
Stokes shift is the difference between positions of the band maxima of the absorption and emission spectra of the same electronic transition. It is named after Irish physicist George Gabriel Stokes.
Photoionization is the physical process in which an ion is formed from the interaction of a photon with an atom or molecule.
Photoexcitation is the production of an excited state of a quantum system by photon absorption. The excited state originates from the interaction between a photon and the quantum system. Photons carry energy that is determined by the wavelengths of the light that carries the photons. Objects that emit light with longer wavelengths, emit photons carrying less energy. In contrast to that, light with shorter wavelengths emit photons with more energy. When the photon interacts with a quantum system, it is therefore important to know what wavelength one is dealing with. A shorter wavelength will transfer more energy to the quantum system than longer wavelengths.
Extreme ultraviolet radiation or high-energy ultraviolet radiation is electromagnetic radiation in the part of the electromagnetic spectrum spanning wavelengths shorter than the hydrogen Lyman-alpha line from 121 nm down to the X-ray band of 10 nm. By the Planck–Einstein equation the EUV photons have energies from 10.26 eV up to 124.24 eV where we enter the X-ray energies. EUV is naturally generated by the solar corona and artificially by plasma, high harmonic generation sources and synchrotron light sources. Since UVC extends to 100 nm, there is some overlap in the terms.
Rydberg ionization spectroscopy is a spectroscopy technique in which multiple photons are absorbed by an atom causing the removal of an electron to form an ion.
Ultrafast laser spectroscopy is a category of spectroscopic techniques using 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.
Doppler cooling is a mechanism that can be used to trap and slow the motion of atoms to cool a substance. The term is sometimes used synonymously with laser cooling, though laser cooling includes other techniques.
Resonance-enhanced multiphoton ionization (REMPI) is a technique applied to the spectroscopy of atoms and small molecules. In practice, a tunable laser can be used to access an excited intermediate state. The selection rules associated with a two-photon or other multiphoton photoabsorption are different from the selection rules for a single photon transition. The REMPI technique typically involves a resonant single or multiple photon absorption to an electronically excited intermediate state followed by another photon which ionizes the atom or molecule. The light intensity to achieve a typical multiphoton transition is generally significantly larger than the light intensity to achieve a single photon photoabsorption. Because of this, subsequent photoabsorption is often very likely. An ion and a free electron will result if the photons have imparted enough energy to exceed the ionization threshold energy of the system. In many cases, REMPI provides spectroscopic information that can be unavailable to single photon spectroscopic methods, for example rotational structure in molecules is easily seen with this technique.
Atmospheric pressure laser ionization is an atmospheric pressure ionization method for mass spectrometry (MS). Laser light in the UV range is used to ionize molecules in a resonance-enhanced multiphoton ionization (REMPI) process. It is a selective and sensitive ionization method for aromatic and polyaromatic compounds. Atmospheric photoionization is the latest in development of atmospheric ionization methods.
An excimer lamp is a source of ultraviolet light based on spontaneous emission of excimer (exciplex) molecules.
Bond softening is an effect of reducing the strength of a chemical bond by strong laser fields. To make this effect significant, the strength of the electric field in the laser light has to be comparable with the electric field the bonding electron "feels" from the nuclei of the molecule. Such fields are typically in the range of 1–10 V/Å, which corresponds to laser intensities 1013–1015 W/cm2. Nowadays, these intensities are routinely achievable from table-top Ti:Sapphire lasers.
Resonance ionization is a process in optical physics used to excite a specific atom beyond its ionization potential to form an ion using a beam of photons irradiated from a pulsed laser light. In resonance ionization, the absorption or emission properties of the emitted photons are not considered, rather only the resulting excited ions are mass-selected, detected and measured. Depending on the laser light source used, one electron can be removed from each atom so that resonance ionization produces an efficient selectivity in two ways: elemental selectivity in ionization and isotopic selectivity in measurement.
1 2 Harris, D. C.; Bertolucci, M. D. (1978). Symmetry and Spectroscopy: An introduction to vibrational and electronic spectroscopy (Reprinted.). Dover Publications. ISBN978-0-486-66144-5.
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