|
Dewar Reactivity Number
In Hückel theory, a Dewar reactivity number, also known as Dewar number, is a measure of the reactivity in aromatic systems. It is used to quantify the difference in energy between the π-system of the original molecule and the intermediate having the incoming electrophile or nucleophile attached. It can be used to study important transformations such as the nitration of conjugated systems from a theoretical perspective. The change in energy during the reaction can be derived by allowing the orbitals nearby the site i of attack to interact with the incoming molecule. A secular determinant can be formulated resulting in the equation: \Delta E=2\beta (a_+a_)=\beta N_i where β is the Huckel interaction parameter and ar and as are the coefficients of the highest energy molecular orbital at nearby sites r and s respectively. Dewar's reactivity number is then defined as N_i=2(a_+a_). Clearly, the smaller the value of Ni, the less the destabilization energy in going towards the tr ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Hückel Theory
Hückel or Huckel may refer to: * Erich Hückel (1896-1980), German physicist and chemist ** Debye–Hückel equation (named after Peter Debye and Erich Hückel), in chemistry, a method of calculating activity coefficients ** Hückel method (named after Erich Hückel), a method for the determination of energies of molecular orbitals *** Extended Hückel method The extended Hückel method is a semiempirical quantum chemistry method, developed by Roald Hoffmann since 1963. It is based on the Hückel method but, while the original Hückel method only considers pi orbitals, the extended method also includes ..., considers also sigma orbitals (whereas the original Hückel method only considers pi orbitals) ** Hückel's rule (named after Erich Hückel), a method of determining aromaticity in organic molecules * (1895-1973), German chemist * (born 1936), German diplomat, Ambassador of the GDR in Chad {{disambig ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Aromaticity
In chemistry, aromaticity is a chemical property of cyclic (ring-shaped), ''typically'' planar (flat) molecular structures with pi bonds in resonance (those containing delocalized electrons) that gives increased stability compared to saturated compounds having single bonds, and other geometric or connective non-cyclic arrangements with the same set of atoms. Aromatic rings are very stable and do not break apart easily. Organic compounds that are not aromatic are classified as aliphatic compounds—they might be cyclic, but only aromatic rings have enhanced stability. The term ''aromaticity'' with this meaning is historically related to the concept of having an aroma, but is a distinct property from that meaning. Since the most common aromatic compounds are derivatives of benzene (an aromatic hydrocarbon common in petroleum and its distillates), the word ''aromatic'' occasionally refers informally to benzene derivatives, and so it was first defined. Nevertheless, man ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Reaction Intermediate
In chemistry, a reaction intermediate or an intermediate is a molecular entity that is formed from the reactants (or preceding intermediates) but is consumed in further reactions in stepwise chemical reactions that contain multiple elementary steps. Intermediates are the reaction product of one elementary step, but do not appear in the chemical equation for an overall chemical equation. For example, consider this hypothetical stepwise reaction: :A + B -> C + D The reaction includes two elementary steps: :A + B -> X :X -> C + D In this example, X is a reaction intermediate. IUPAC definition The IUPAC Gold Book defines an ''intermediate'' as a compound that has a lifetime greater than a molecular vibration that is formed (directly or indirectly) from the reactants and reacts further to give (either directly or indirectly) the products of a chemical reaction. The lifetime condition distinguishes true, chemically distinct intermediates from vibrational states or such transiti ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Electrophile
In chemistry, an electrophile is a chemical species that forms bonds with nucleophiles by accepting an electron pair. Because electrophiles accept electrons, they are Lewis acids. Most electrophiles are positively charged, have an atom that carries a partial positive charge, or have an atom that does not have an octet of electrons. Electrophiles mainly interact with nucleophiles through addition and substitution reactions. Frequently seen electrophiles in organic syntheses include cations such as H+ and NO+, polarized neutral molecules such as HCl, alkyl halides, acyl halides, and carbonyl compounds, polarizable neutral molecules such as Cl2 and Br2, oxidizing agents such as organic peracids, chemical species that do not satisfy the octet rule such as carbenes and radicals, and some Lewis acids such as BH3 and DIBAL. Organic chemistry Addition of halogens These occur between alkenes and electrophiles, often halogens as in halogen addition reactions. Comm ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Nucleophile
In chemistry, a nucleophile is a chemical species that forms bonds by donating an electron pair. All molecules and ions with a free pair of electrons or at least one pi bond can act as nucleophiles. Because nucleophiles donate electrons, they are Lewis bases. ''Nucleophilic'' describes the affinity of a nucleophile to bond with positively charged atomic nuclei. Nucleophilicity, sometimes referred to as nucleophile strength, refers to a substance's nucleophilic character and is often used to compare the affinity of atoms. Neutral nucleophilic reactions with solvents such as alcohols and water are named solvolysis. Nucleophiles may take part in nucleophilic substitution, whereby a nucleophile becomes attracted to a full or partial positive charge, and nucleophilic addition. Nucleophilicity is closely related to basicity. History The terms ''nucleophile'' and ''electrophile'' were introduced by Christopher Kelk Ingold in 1933, replacing the terms ''anionoid'' and ''cation ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Nitration
In organic chemistry, nitration is a general class of chemical processes for the introduction of a nitro group into an organic compound. The term also is applied incorrectly to the different process of forming nitrate esters between alcohols and nitric acid (as occurs in the synthesis of nitroglycerin). The difference between the resulting molecular structures of nitro compounds and nitrates is that the nitrogen atom in nitro compounds is directly bonded to a non-oxygen atom (typically carbon or another nitrogen atom), whereas in nitrate esters (also called organic nitrates), the nitrogen is bonded to an oxygen atom that in turn usually is bonded to a carbon atom (nitrito group). There are many major industrial applications of nitration in the strict sense; the most important by volume are for the production of nitroaromatic compounds such as nitrobenzene. Nitration reactions are notably used for the production of explosives, for example the conversion of guanidine to nitr ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Theoretical Chemistry
Theoretical chemistry is the branch of chemistry which develops theoretical generalizations that are part of the theoretical arsenal of modern chemistry: for example, the concepts of chemical bonding, chemical reaction, valence, the surface of potential energy, molecular orbitals, orbital interactions, and molecule activation. Overview Theoretical chemistry unites principles and concepts common to all branches of chemistry. Within the framework of theoretical chemistry, there is a systematization of chemical laws, principles and rules, their refinement and detailing, the construction of a hierarchy. The central place in theoretical chemistry is occupied by the doctrine of the interconnection of the structure and properties of molecular systems. It uses mathematical and physical methods to explain the structures and dynamics of chemical systems and to correlate, understand, and predict their thermodynamic and kinetic properties. In the most general sense, it is explanation ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Molecular Orbital
In chemistry, a molecular orbital is a mathematical function describing the location and wave-like behavior of an electron in a molecule. This function can be used to calculate chemical and physical properties such as the probability of finding an electron in any specific region. The terms ''atomic orbital'' and ''molecular orbital'' were introduced by Robert S. Mulliken in 1932 to mean ''one-electron orbital wave functions''. At an elementary level, they are used to describe the ''region'' of space in which a function has a significant amplitude. In an isolated atom, the orbital electrons' location is determined by functions called atomic orbitals. When multiple atoms combine chemically into a molecule, the electrons' locations are determined by the molecule as a whole, so the atomic orbitals combine to form molecular orbitals. The electrons from the constituent atoms occupy the molecular orbitals. Mathematically, molecular orbitals are an approximate solution to the Schrö ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Secular Determinant
In linear algebra, the characteristic polynomial of a square matrix is a polynomial which is invariant under matrix similarity and has the eigenvalues as roots. It has the determinant and the trace of the matrix among its coefficients. The characteristic polynomial of an endomorphism of a finite-dimensional vector space is the characteristic polynomial of the matrix of that endomorphism over any base (that is, the characteristic polynomial does not depend on the choice of a basis). The characteristic equation, also known as the determinantal equation, is the equation obtained by equating the characteristic polynomial to zero. In spectral graph theory, the characteristic polynomial of a graph is the characteristic polynomial of its adjacency matrix. Motivation In linear algebra, eigenvalues and eigenvectors play a fundamental role, since, given a linear transformation, an eigenvector is a vector whose direction is not changed by the transformation, and the corresponding eigenval ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Transition State
In chemistry, the transition state of a chemical reaction is a particular configuration along the reaction coordinate. It is defined as the state corresponding to the highest potential energy along this reaction coordinate. It is often marked with the double dagger ‡ symbol. As an example, the transition state shown below occurs during the SN2 reaction of bromoethane with a hydroxide anion: The activated complex of a reaction can refer to either the transition state or to other states along the reaction coordinate between reactants and products, especially those close to the transition state. Peter Atkins and Julio de Paula, ''Physical Chemistry'' (8th ed., W.H. Freeman 2006), p.809 According to the transition state theory, once the reactants have passed through the transition state configuration, they always continue to form products. History of concept The concept of a transition state has been important in many theories of the rates at which chemical react ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Alternant Hydrocarbon
An alternant hydrocarbon is any conjugated hydrocarbon system which does not possess an odd-membered ring. For such systems it is possible to undertake a starring process, in which the carbon atoms are divided into two sets: all the carbons in one set are marked with a star such that no two starred or unstarred atoms are bonded to each other. Here the starred set contains the highest number of atoms. When this condition is met, the secular determinant in the Hückel approximation has a simpler form, since cross-diagonal elements between atoms in the same set are necessarily 0. Alternant hydrocarbons display three very interesting properties: *The molecular orbital energies for the π system are paired, that is for an orbital of energy E=\alpha +x\beta there is one of energy E=\alpha-x\beta. *The coefficients of two paired molecular orbitals are the same at the same site, except for a sign change in the unstarred set. *The population or electron density at all sites is equal to un ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Molecular Physics
Molecular physics is the study of the physical properties of molecules and molecular dynamics. The field overlaps significantly with physical chemistry, chemical physics, and quantum chemistry. It is often considered as a sub-field of atomic, molecular, and optical physics. Research groups studying molecular physics are typically designated as one of these other fields. Molecular physics addresses phenomena due to both molecular structure and individual atomic processes within molecules. Like atomic physics, it relies on a combination of classical and quantum mechanics to describe interactions between electromagnetic radiation and matter. Experiments in the field often rely heavily on techniques borrowed from atomic physics, such as spectroscopy and scattering. Molecular Structure In a molecule, both the electrons and nuclei experience similar-scale forces from the Coulomb interaction. However, the nuclei remain at nearly fixed locations in the molecule while the electrons ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
.png "Click for more on -> Aromaticity")
