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Radical Pair Mechanism
CIDNP (chemically induced dynamic nuclear polarization), often pronounced like "kidnip", is a nuclear magnetic resonance (NMR) technique that is used to study chemical reactions that involve radicals. It detects the non-Boltzmann (non-thermal) nuclear spin state distribution produced in these reactions as enhanced absorption or emission signals. CIDNP was discovered in 1967 by Bargon and Fischer, and, independently, by Ward and Lawler. Early theories were based on dynamic nuclear polarisation (hence the name) using the Overhauser effect. The subsequent experiments, however, have found that in many cases DNP fails to explain CIDNP polarization phase. In 1969 an alternative explanation which relies on the nuclear spins affecting the probability of a radical pair recombining or separating. It is related to chemically induced dynamic electron polarization (CIDEP) insofar as the radical-pair mechanism explains both phenomena. Concept and experimental set-up The effect is detected by ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Nuclear Magnetic Resonance
Nuclear magnetic resonance (NMR) is a physical phenomenon in which nuclei in a strong constant magnetic field are disturbed by a weak oscillating magnetic field (in the near field) and respond by producing an electromagnetic signal with a frequency characteristic of the magnetic field at the nucleus. This process occurs near resonance, when the oscillation frequency matches the intrinsic frequency of the nuclei, which depends on the strength of the static magnetic field, the chemical environment, and the magnetic properties of the isotope involved; in practical applications with static magnetic fields up to ca. 20 tesla, the frequency is similar to VHF and UHF television broadcasts (60–1000 MHz). NMR results from specific magnetic properties of certain atomic nuclei. High-resolution nuclear magnetic resonance spectroscopy is widely used to determine the structure of organic molecules in solution and study molecular physics and crystals as well as non-crysta ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Photon
A photon () is an elementary particle that is a quantum of the electromagnetic field, including electromagnetic radiation such as light and radio waves, and the force carrier for the electromagnetic force. Photons are massless particles that can move no faster than the speed of light measured in vacuum. The photon belongs to the class of boson particles. As with other elementary particles, photons are best explained by quantum mechanics and exhibit wave–particle duality, their behavior featuring properties of both waves and particles. The modern photon concept originated during the first two decades of the 20th century with the work of Albert Einstein, who built upon the research of Max Planck. While Planck was trying to explain how matter and electromagnetic radiation could be in thermal equilibrium with one another, he proposed that the energy stored within a material object should be regarded as composed of an integer number of discrete, equal-sized parts. To explain the pho ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Chemical Kinetics
Chemical kinetics, also known as reaction kinetics, is the branch of physical chemistry that is concerned with understanding the rates of chemical reactions. It is different from chemical thermodynamics, which deals with the direction in which a reaction occurs but in itself tells nothing about its rate. Chemical kinetics includes investigations of how experimental conditions influence the speed of a chemical reaction and yield information about the reaction's mechanism and transition states, as well as the construction of mathematical models that also can describe the characteristics of a chemical reaction. History The pioneering work of chemical kinetics was done by German chemist Ludwig Wilhelmy in 1850. He experimentally studied the rate of inversion of sucrose and he used integrated rate law for the determination of the reaction kinetics of this reaction. His work was noticed 34 years later by Wilhelm Ostwald. In 1864, Peter Waage and Cato Guldberg published the law ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Electron Transfer Reaction
Electron transfer (ET) occurs when an electron relocates from an atom, ion, or molecule, to another such chemical entity. ET describes the mechanism by which electrons are transferred in redox reactions. Electrochemical processes are ET reactions. ET reactions are relevant to photosynthesis and respiration and commonly involve transition metal complexes. In organic chemistry ET is a step in some industrial polymerization reactions. It is foundational to photoredox catalysis. Classes of electron transfer Inner-sphere electron transfer In inner-sphere ET, two redox centers are covalently linked during the ET. This bridge can be permanent, in which case the electron transfer event is termed intramolecular electron transfer. More commonly, however, the covalent linkage is transitory, forming just prior to the ET and then disconnecting following the ET event. In such cases, the electron transfer is termed intermolecular electron transfer. A famous example of an inner sphere ET proces ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Diffusion-controlled Reaction
Diffusion-controlled (or diffusion-limited) chemical reaction, reactions are reactions in which the reaction rate is equal to the rate of transport of the reactants through the reaction medium (usually a solution). The process of chemical reaction can be considered as involving the diffusion of reactants until they encounter each other in the right stoichiometry and form an activated complex which can form the product species. The observed rate of chemical reactions is, generally speaking, the rate of the slowest or "rate determining" step. In diffusion controlled reactions the formation of products from the activated complex is much faster than the diffusion of reactants and thus the rate is governed by collision frequency. Diffusion control is rare in the gas phase, where rates of diffusion of molecules are generally very high. Diffusion control is more likely in solution where diffusion of reactants is slower due to the greater number of collisions with solvent molecules. React ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Polycyclic Aromatic Hydrocarbon
A Polycyclic aromatic hydrocarbon (PAH) is any member of a class of organic compounds that is composed of multiple fused aromatic rings. Most are produced by the incomplete combustion of organic matter— by engine exhaust fumes, tobacco, incinerators, in roasted meats and cereals, or when biomass burns at lower temperatures as in forest fires. The simplest representative is naphthalene, having two aromatic rings, and the three-ring compounds anthracene and phenanthrene. PAHs are uncharged, non-polar and planar. Many are colorless. Many of them are also found in fossil fuel deposits such as coal and in petroleum. Exposure to PAHs can lead to different types of cancer, to fetal development complications, and to cardiovascular issues. Polycyclic aromatic hydrocarbons are discussed as possible starting materials for abiotic syntheses of materials required by the earliest forms of life. Nomenclature and structure The terms polyaromatic hydrocarbon, or polynuclear aromatic hydro ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Phenol
Phenol (also known as carbolic acid, phenolic acid, or benzenol) is an aromatic organic compound with the molecular formula . It is a white crystalline solid that is volatile and can catch fire. The molecule consists of a phenyl group () bonded to a hydroxy group (). Mildly acidic, it requires careful handling because it can cause chemical burns. It is acutely toxic and is considered a health hazard. Phenol was first extracted from coal tar, but today is produced on a large scale (about 7 million tonnes a year) from petroleum-derived feedstocks. It is an important industrial commodity as a precursor to many materials and useful compounds, and is a liquid when manufactured. It is primarily used to synthesize plastics and related materials. Phenol and its chemical derivatives are essential for production of polycarbonates, epoxies, explosives such as picric acid, Bakelite, nylon, detergents, herbicides such as phenoxy herbicides, and numerous pharmaceuti ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Ionization Potential
In physics and chemistry, ionization energy (IE) is the minimum energy required to remove the most loosely bound electron of an isolated gaseous atom, positive ion, or molecule. The first ionization energy is quantitatively expressed as :X(g) + energy ⟶ X+(g) + e− where X is any atom or molecule, X+ is the resultant ion when the original atom was stripped of a single electron, and e− is the removed electron. Ionization energy is positive for neutral atoms, meaning that the ionization is an endothermic process. Roughly speaking, the closer the outermost electrons are to the nucleus of the atom, the higher the atom's ionization energy. In physics, ionization energy (IE) is usually expressed in electronvolts (eV) or joules (J). In chemistry, it is expressed as the energy to ionize a mole of atoms or molecules, usually as kilojoules per mole (kJ/mol) or kilocalories per mole (kcal/mol). Comparison of ionization energies of atoms in the periodic table reveals two period ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Electron Affinity
The electron affinity (''E''ea) of an atom or molecule is defined as the amount of energy released when an electron attaches to a neutral atom or molecule in the gaseous state to form an anion. ::X(g) + e− → X−(g) + energy This differs by sign from the energy change of electron capture ionization. The electron affinity is positive when energy is released on electron capture. In solid state physics, the electron affinity for a surface is defined somewhat differently ( see below). Measurement and use of electron affinity This property is used to measure atoms and molecules in the gaseous state only, since in a solid or liquid state their energy levels would be changed by contact with other atoms or molecules. A list of the electron affinities was used by Robert S. Mulliken to develop an electronegativity scale for atoms, equal to the average of the electrons affinity and ionization potential. Other theoretical concepts that use electron affinity include electronic chem ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Triplet State
In quantum mechanics, a triplet state, or spin triplet, is the quantum state of an object such as an electron, atom, or molecule, having a quantum spin ''S'' = 1. It has three allowed values of the spin's projection along a given axis ''m''S = −1, 0, or +1, giving the name "triplet". Spin, in the context of quantum mechanics, is not a mechanical rotation but a more abstract concept that characterizes a particle's intrinsic angular momentum. It is particularly important for systems at atomic length scales, such as individual atoms, protons, or electrons. A triplet state occurs in cases where the spins of two unpaired electrons, each having spin ''s'' = , align to give ''S'' = 1, in contrast to the more common case of two electrons aligning oppositely to give ''S'' = 0, a spin singlet. Most molecules encountered in daily life exist in a singlet state because all of their electrons are paired, but molecular oxygen is an exception. At room temperature, O2 exists in a triplet ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Intersystem Crossing
Intersystem crossing (ISC) is an isoenergetic radiationless process involving a transition between the two electronic states with different spin multiplicity. Excited singlet and triplet states When an electron in a molecule with a singlet ground state is excited (''via'' absorption of radiation) to a higher energy level, either an excited singlet state or an excited triplet state will form. Singlet state is a molecular electronic state such that all electron spins are paired. That is, the spin of the excited electron is still paired with the ground state electron (a pair of electrons in the same energy level must have opposite spins, per the Pauli exclusion principle). In a triplet state the excited electron is no longer paired with the ground state electron; that is, they are parallel (same spin). Since excitation to a triplet state involves an additional "forbidden" spin transition, it is less probable that a triplet state will form when the molecule absorbs radiation. ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Quantum Yield
In particle physics, the quantum yield (denoted ) of a radiation-induced process is the number of times a specific event occurs per photon absorbed by the system. \Phi(\lambda)=\frac Applications Fluorescence spectroscopy The fluorescence quantum yield is defined as the ratio of the number of photons emitted to the number of photons absorbed.Lakowicz, Joseph R. ''Principles of Fluorescence Spectroscopy'' (Kluwer Academic / Plenum Publishers 1999) p.10. \Phi = \frac Fluorescence quantum yield is measured on a scale from 0 to 1.0, but is often represented as a percentage. A quantum yield of 1.0 (100%) describes a process where each photon absorbed results in a photon emitted. Substances with the largest quantum yields, such as rhodamines, display the brightest emissions; however, compounds with quantum yields of 0.10 are still considered quite fluorescent. Quantum yield is defined by the fraction of excited state fluorophores that decay through fluorescence: \Phi_f = \f ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
