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Baird's Rule
In organic chemistry, Baird's rule estimates whether the lowest triplet state of planar, cyclic structures will have aromatic properties or not. The quantum mechanical basis for its formulation was first worked out by physical chemist N. Colin Baird at the University of Western Ontario in 1972. The lowest triplet state of an annulene is, according to Baird's rule, aromatic when it has 4''n'' π-electrons and antiaromatic when the π-electron count is 4''n'' + 2, where ''n'' is any positive integer. This trend is opposite to that predicted by Hückel's rule for the ground state, which is usually the lowest singlet state (S0). Baird's rule has thus become known as the photochemical analogue of Hückel's rule. Through various theoretical investigations, this rule has also been found to extend to the lowest lying singlet excited state (S1) of small annulenes. See also * Möbius–Hückel concept * Möbius aromaticity In organic chemistry, Möbius aromaticity is a special type of a ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Organic Chemistry
Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J.; Greeves, N. and Warren, S. (2012) ''Organic Chemistry''. Oxford University Press. pp. 1–15. . Study of structure determines their structural formula. Study of properties includes physical and chemical properties, and evaluation of chemical reactivity to understand their behavior. The study of organic reactions includes the chemical synthesis of natural products, drugs, and polymers, and study of individual organic molecules in the laboratory and via theoretical ( in silico) study. The range of chemicals studied in organic chemistry includes hydrocarbons (compounds containing only carbon and hydrogen) as well as compounds based on carbon, but also containing other elements, especially oxygen, nitrogen, sulfur, phosphorus (included in ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Antiaromaticity
Antiaromaticity is a chemical property of a cyclic molecule with a π electron system that has higher energy, i.e., it is less stable due to the presence of 4n delocalised (π or lone pair) electrons in it, as opposed to aromaticity. Unlike aromatic compounds, which follow Hückel's rule ( ''n''+2π electrons) and are highly stable, antiaromatic compounds are highly unstable and highly reactive. To avoid the instability of antiaromaticity, molecules may change shape, becoming non-planar and therefore breaking some of the π interactions. In contrast to the diamagnetic ring current present in aromatic compounds, antiaromatic compounds have a paramagnetic ring current, which can be observed by NMR spectroscopy. Examples of antiaromatic compounds are pentalene (A), biphenylene (B), cyclopentadienyl cation (C). The prototypical example of antiaromaticity, cyclobutadiene, is the subject of debate, with some scientists arguing that antiaromaticity is not a major factor contributing t ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Möbius Aromaticity
In organic chemistry, Möbius aromaticity is a special type of aromaticity believed to exist in a number of organic molecules. In terms of molecular orbital theory these compounds have in common a monocyclic array of molecular orbitals in which there is an odd number of out-of-phase overlaps, the opposite pattern compared to the aromatic character to Hückel's rule, Hückel systems. The nodal plane of the orbitals, viewed as a ribbon, is a Möbius strip, rather than a cylinder, hence the name. The pattern of orbital energies is given by a rotated Möbius–Hückel concept, Frost circle (with the edge of the polygon on the bottom instead of a vertex), so systems with 4''n'' electrons are aromatic, while those with 4''n'' + 2 electrons are anti-aromatic/non-aromatic. Due to incrementally twisted nature of the orbitals of a Möbius aromatic system, stable Möbius aromatic molecules need to contain at least 8 electrons, although 4 electron Möbius aromatic transition states are well k ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Möbius–Hückel Concept
In chemistry, the Möbius–Hückel treatment is a methodology used to predict whether a reaction is allowed or forbidden. It is often used alone with the Woodward–Hoffmann approach. The description in this article uses the plus-minus sign notation for parity as shorthand while proceeding around a cycle of orbitals in a molecule or system, while the Woodward–Hoffmann methodology uses a large number of rules with the same consequences. Introduction One year following the Woodward–Hoffmann and Longuet-Higgins–Abrahmson publications, it was noted by Zimmerman that both transition states and stable molecules sometimes involved a Möbius array of basis orbitals. The Möbius–Hückel treatment provides an alternative to the Woodward–Hoffmann one. In contrast to the Woodward–Hoffmann approach the Möbius–Hückel treatment is not dependent on symmetry and only requires counting the number of plus-minus sign inversions in proceeding around the cyclic array of orbitals. Wh ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Photochemistry
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 (wavelength from 100 to 400 nm), visible light (400–750 nm) or infrared radiation (750–2500 nm). In nature, photochemistry is of immense importance as it is the basis of photosynthesis, vision, and the formation of vitamin D with sunlight. Photochemical reactions proceed differently than temperature-driven reactions. Photochemical paths access high energy intermediates that cannot be generated thermally, thereby overcoming large activation barriers in a short period of time, and allowing reactions otherwise inaccessible by thermal processes. Photochemistry can also be destructive, as illustrated by the photodegradation of plastics. Concept Grotthuss–Draper law and Stark-Einstein law Photoexcitation is the first step in a photochemical process where the reactant is elevated ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Singlet State
In quantum mechanics, a singlet state usually refers to a system in which all electrons are paired. The term 'singlet' originally meant a linked set of particles whose net angular momentum is zero, that is, whose overall spin quantum number s=0. As a result, there is only one spectral line of a singlet state. In contrast, a doublet state contains one unpaired electron and shows splitting of spectral lines into a doublet; and a triplet state has two unpaired electrons and shows threefold splitting of spectral lines. History Singlets and the related spin concepts of doublets and triplets occur frequently in atomic physics and nuclear physics, where one often needs to determine the total spin of a collection of particles. Since the only observed fundamental particle with zero spin is the extremely inaccessible Higgs boson, singlets in everyday physics are necessarily composed of sets of particles whose individual spins are non-zero, e.g. or 1. The origin of the term "singlet" is ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Ground State
The ground state of a quantum-mechanical system is its stationary state of lowest energy; the energy of the ground state is known as the zero-point energy of the system. An excited state is any state with energy greater than the ground state. In quantum field theory, the ground state is usually called the vacuum state or the vacuum. If more than one ground state exists, they are said to be degenerate. Many systems have degenerate ground states. Degeneracy occurs whenever there exists a unitary operator that acts non-trivially on a ground state and commutes with the Hamiltonian of the system. According to the third law of thermodynamics, a system at absolute zero temperature exists in its ground state; thus, its entropy is determined by the degeneracy of the ground state. Many systems, such as a perfect crystal lattice, have a unique ground state and therefore have zero entropy at absolute zero. It is also possible for the highest excited state to have absolute zero temper ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Hückel's Rule
In organic chemistry, Hückel's rule predicts that a planar ring molecule will have aromatic properties if it has 4''n'' + 2 π electrons, where ''n'' is a non-negative integer. The quantum mechanical basis for its formulation was first worked out by physical chemist Erich Hückel in 1931. The succinct expression as the 4''n'' + 2 rule has been attributed to W. v. E. Doering (1951), although several authors were using this form at around the same time. In agreement with the Möbius–Hückel concept, a cyclic ring molecule follows Hückel's rule when the number of its π-electrons equals 4''n'' + 2, although clearcut examples are really only established for values of ''n'' = 0 up to about ''n'' = 6. Hückel's rule was originally based on calculations using the Hückel method, although it can also be justified by considering a particle in a ring system, by the LCAO method and by the Pariser–Parr–Pople method. Aromatic com ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Integer
An integer is the number zero (), a positive natural number (, , , etc.) or a negative integer with a minus sign (−1, −2, −3, etc.). The negative numbers are the additive inverses of the corresponding positive numbers. In the language of mathematics, the set of integers is often denoted by the boldface or blackboard bold \mathbb. The set of natural numbers \mathbb is a subset of \mathbb, which in turn is a subset of the set of all rational numbers \mathbb, itself a subset of the real numbers \mathbb. Like the natural numbers, \mathbb is countably infinite. An integer may be regarded as a real number that can be written without a fractional component. For example, 21, 4, 0, and −2048 are integers, while 9.75, , and are not. The integers form the smallest group and the smallest ring containing the natural numbers. In algebraic number theory, the integers are sometimes qualified as rational integers to distinguish them from the more general algebraic integers ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Pi Electron
In chemistry, pi bonds (π bonds) are covalent chemical bonds, in each of which two lobes of an orbital on one atom overlap with two lobes of an orbital on another atom, and in which this overlap occurs laterally. Each of these atomic orbitals has an electron density of zero at a shared nodal plane that passes through the two bonded nuclei. This plane also is a nodal plane for the molecular orbital of the pi bond. Pi bonds can form in double and triple bonds but do not form in single bonds in most cases. The Greek letter π in their name refers to p orbitals, since the orbital symmetry of the pi bond is the same as that of the p orbital when seen down the bond axis. One common form of this sort of bonding involves p orbitals themselves, though d orbitals also engage in pi bonding. This latter mode forms part of the basis for metal-metal multiple bonding. Pi bonds are usually weaker than sigma bonds. The C-C double bond, composed of one sigma and one pi bond, has a bond ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Triplet State
In quantum mechanics, a triplet is a quantum state of a system with a spin of quantum number =1, such that there are three allowed values of the spin component, = −1, 0, and +1. 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. Almost all molecules encountered in daily life exist in a singlet state, but molecular oxygen is an exception. At room temperature, O2 exists in a triplet state, which can only undergo a chemical reaction by making the forbidden transition into a singlet state. This makes it kinetically nonreactive despite being thermodynamically one of the strongest oxidants. Photochemical or thermal activation can bring it into the singlet state, which makes it kinetically as well as thermodynamically a very strong oxidant. __TOC__ Two spin ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Annulene
Annulenes are monocyclic hydrocarbons that contain the maximum number of non-cumulated or conjugated double bonds (' mancude'). They have the general formula CnHn (when ''n'' is an even number) or C''n''H''n''+1 (when ''n'' is an odd number). The IUPAC naming conventions are that annulenes with 7 or more carbon atoms are named as 'n''nnulene, where ''n'' is the number of carbon atoms in their ring, though sometimes the smaller annulenes are referred to using the same notation, and benzene is sometimes referred to simply as annulene. The first three even annulenes are cyclobutadiene, benzene, and cyclooctatetraene ( nnulene). Some annulenes, namely cyclobutadiene, cyclodecapentaene ( 0nnulene), cyclododecahexaene ( 2nnulene) and cyclotetradecaheptaene ( 4nnulene), are unstable, with cyclobutadiene extremely so. In the related annulynes, one double bond is replaced by a triple bond. Aromaticity Annulenes may be ''aromatic'' (benzene, nnulene and 8nnulene), ''non-aromat ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
