User:Thecurran91/Chembond

A chemical bond is an interaction between atoms or molecules and allows the formation of polyatomic chemical compounds. A chemical bond is the attraction caused by the electromagnetic force between opposing charges, either between electrons and nuclei, or as the result of a dipole. The strength of bonds varies considerably; there are "strong bonds" such as covalent or ionic bonds and "weak bonds" such as dipole-dipole interactions, the London dispersion force and hydrogen bonding.

The different types of bond give rise to different characteristics in molecules. Molecules which are primarily bonded covalently (such as hydrocarbons are often immiscible in water but will dissolve readily in organic or non-polar solvents such as hexane. They will feature low boiling points with respect to polar analogues due to the lack of dipole-dipole interactions. Ionic compounds, such as metal salts, are often crystalline compounds which are partially or fully miscible in water. They have extremely high melting points due to the strong electrostatic forces holding the opposing ions together.

Intermolecular (weak) bonds play a significant role in determining the physical characteristics of non-ionic compounds. Typically, a non-polar molecule (for example, butane) will only form the very weak London dispersion forces between molecules; meaning it will have a low boiling point and be volatile. Molecules with permanent dipoles such as fluoromethane will have higher boiling points than the parent hydrocarbon because of dipole-dipole interactions because of the polar C-F bond. Some molecules will be able to hydrogen bond with others, due to the presence of a H-F, H-N or H-O bond, and will have very high boiling points.

Although the attractive forces are governed by quantum electrodynamics,^[1] there are many more simple theories which can be used in lieu such as valence bond theory and molecular orbital theory.

History

Early speculations into the nature of the chemical bond, from as early as the 12th century, supposed that certain types of chemical species were joined by a type of chemical affinity. In 1704, Isaac Newton famously outlined his atomic bonding theory, in "Query 31" of his Opticks, whereby atoms attach to each other by some "force". Specifically, after acknowledging the various popular theories in vogue at the time, of how atoms were reasoned to attach to each other, i.e. “hooked atoms”, “glued together by rest”, or “stuck together by conspiring motions”, Newton states that he would rather infer from their cohesion, that "particles attract one another by some force, which in immediate contact is exceedingly strong, at small distances performs the chemical operations, and reaches not far from the particles with any sensible effect."

In 1819, on the heels of the invention of the voltaic pile, Jöns Jakob Berzelius developed a theory of chemical combination stressing the electronegative and electropositive character of the combining atoms. By the mid 19th century, Edward Frankland, F.A. Kekule, A.S. Couper, A.M. Butlerov, and Hermann Kolbe, building on the theory of radicals, developed the theory of valency, originally called “combining power”, in which compounds were joined owing to an attraction of positive and negative poles. In 1916, chemist Gilbert N. Lewis developed the concept of the electron-pair bond, in which two atoms may share one to six electrons, thus forming the single electron bond, a single bond, a double bond, or a triple bond; in Lewis's own words, "An electron may form a part of the shell of two different atoms and cannot be said to belong to either one exclusively."^[2]

That same year, Walther Kossel put forward a theory similar to Lewis' only his model assumed complete transfers of electrons between atoms, and was thus a model of ionic bonds. Both Lewis and Kossel structured their bonding models on that of Abegg's rule (1904).

In 1927, the first mathematically complete quantum description of a simple chemical bond, i.e. that produced by one electron in the hydrogen molecular ion, H₂⁺, was derived by the Danish physicist Oyvind Burrau.^[3] This work showed that the quantum approach to chemical bonds could be fundamentally and quantitatively correct, but the mathematical methods used could not be extended to molecules containing more than one electron. A more practical, albeit less quantitative, approach was put forward in the same year by Walter Heitler and Fritz London. The Heitler-London method forms the basis of what is now called valence bond theory. In 1929, the linear combination of atomic orbitals molecular orbital method (LCAO) approximation was introduced by Sir John Lennard-Jones, who also suggested methods to derive electronic structures of molecules of F₂ (fluorine) and O₂ (oxygen) molecules, from basic quantum principles. This molecular orbital theory represented a covalent bond as a orbitals formed by combining the quantum mechanical Schrödinger atomic orbitals which had been hypothesized for electrons in single atoms. The equations for bonding electrons in multi-electron atoms could not be solved to mathematical perfection (i.e., analytically), but approximations for them still gave many good qualitative predictions and results. Most quantitative calculations in modern quantum chemistry use either valence bond or molecular orbital theory as a starting point, although a third approach, Density Functional Theory, has become increasingly popular in recent years.

In 1935, H. H. James and A. S. Coolidge carried out a calculation on the dihydrogen molecule that, unlike all previous calculation which used functions only of the distance of the electron from the atomic nucleus, used functions which also explicitly added the distance between the two electrons.^[4] With up to 13 adjustable parameters they obtained a result very close to the experimental result for the dissociation energy. Later extensions have used up to 54 parameters and give excellent agreement with experiment. This calculation convinced the scientific community that quantum theory could give agreement with experiment. However this approach has none of the physical pictures of the valence bond and molecular orbital theories and is difficult to extend to larger molecules.

Valence bond theory

In the year 1927, valence bond theory was formulated which argued essentially that a chemical bond forms when two valence electrons, in their respective atomic orbitals, work or function to hold two nuclei together, by virtue of system energy lowering effects. In 1931, building on this theory, chemist Linus Pauling published what some consider one of the most important papers in the history of chemistry: “On the Nature of the Chemical Bond”. In this paper, building on the works of Lewis, and the valence bond theory (VB) of Heitler and London, and his own earlier work, he presented six rules for the shared electron bond, the first three of which were already generally known:

1. The electron-pair bond forms through the interaction of an unpaired electron on each of two atoms.

2. The spins of the electrons have to be opposed.

3. Once paired, the two electrons cannot take part in additional bonds.

His last three rules were new:

4. The electron-exchange terms for the bond involves only one wave function from each atom.

5. The available electrons in the lowest energy level form the strongest bonds.

6. Of two orbitals in an atom, the one that can overlap the most with an orbital from another atom will form the strongest bond, and this bond will tend to lie in the direction of the concentrated orbital.

Building on this article, Pauling’s 1939 textbook: On the Nature of the Chemical Bond would become what some have called the “bible” of modern chemistry. This book helped experimental chemists to understand the impact of quantum theory on chemistry. However, the later edition in 1959 failed to address adequately the problems that appeared to be better understood by molecular orbital theory. The impact of valence theory declined during the 1960s and 1970's as molecular orbital theory grew in popularity and was implemented in many large computer programs. Since the 1980s, the more difficult problems of implementing valence bond theory into computer programs have been largely solved and valence bond theory has seen a resurgence.

Comparison of valence bond and molecular orbital theory

In some respects valence bond theory is superior to molecular orbital theory. When applied to the simplest two-electron molecule, H₂, valence bond theory, even at the simplest Heitler-London approach, gives a much closer approximation to the bond energy, and it provides a much more accurate representation of the behavior of the electrons as chemical bonds are formed and broken. In contrast simple molecular orbital theory predicts that the hydrogen molecule dissociates into a linear superposition of hydrogen atoms and positive and negative hydrogen ions, a completely unphysical result. This explains in part why the curve of total energy against interatomic distance for the valence bond method lies above the curve for the molecular orbital method at all distances and most particularly so for large distances. This situation arises for all homonuclear diatomic molecules and is particularly a problem for F₂, where the minimum energy of the curve with molecular orbital theory is still higher in energy than the energy of two F atoms.

The concepts of hybridization are so versatile, and the variability in bonding in most organic compounds is so modest, that valence bond theory remains an integral part of the vocabulary of organic chemistry. However, the work of Friedrich Hund, Robert Mulliken, and Gerhard Herzberg showed that molecular orbital theory provided a more appropriate description of the spectroscopic, ionization and magnetic properties of molecules. The deficiencies of valence bond theory became apparent when hypervalent molecules (e.g. PF₅) were explained without the use of d orbitals that were crucial to the bonding hybridisation scheme proposed for such molecules by Pauling. Metal complexes and electron deficient compounds (e.g. diborane) also appeared to be well described by molecular orbital theory, although valence bond descriptions have been made.

In the 1930s the two methods strongly competed until it was realised that they are both approximations to a better theory. If we take the simple valence bond structure and mix in all possible covalent and ionic structures arising from a particular set of atomic orbitals, we reach what is called the full configuration interaction wave function. If we take the simple molecular orbital description of the ground state and combine that function with the functions describing all possible excited states using unoccupied orbitals arising from the same set of atomic orbitals, we also reach the full configuration interaction wavefunction. It can be then seen that the simple molecular orbital approach gives too much weight to the ionic structures, while the simple valence bond approach gives too little. This can also be described as saying that the molecular orbital approach is too delocalised, while the valence bond approach is too localised.

The two approaches are now regarded as complementary, each providing its own insights into the problem of chemical bonding. Modern calculations in quantum chemistry usually start from (but ultimately go far beyond) a molecular orbital rather than a valence bond approach, not because of any intrinsic superiority in the former but rather because the MO approach is more readily adapted to numerical computations. However better valence bond programs are now available.

Bonds in chemical formula

The 3-dimensionality of atoms and molecules makes it difficult to use a single technique for indicating orbitals and bonds. In molecular formulae the chemical bonds (binding orbitals) between atoms are indicated by various different methods according to the type of discussion. Sometimes, they are completely neglected. For example, in organic chemistry chemists are sometimes concerned only with the functional groups of the molecule. Thus, the molecular formula of ethanol (a compound in alcoholic beverages) may be written in a paper in conformational, 3-dimensional, full 2-dimensional (indicating every bond with no 3-dimensional directions), compressed 2-dimensional (CH₃–CH₂–OH), separating the functional group from another part of the molecule (C₂H₅OH), or by its atomic constituents (C₂H₆O), according to what is discussed. Sometimes, even the non-bonding valence shell electrons (with the 2-dimensional approximate directions) are marked, i.e. for elemental carbon _.^'C^'. Some chemists may also mark the respective orbitals, i.e. the hypothetical ethene⁻⁴ anion (_\^/C=C_/^\ ⁻⁴) indicating the possibility of bond formation.

Strong chemical bonds

Bond	Length (pm)	Energy (kJ/mol)
Typical bond lengths in pm and bond energies in kJ/mol. Bond lengths can be converted to Å by division by 100 (1 Å = 100 pm). Data taken from [1].
H — Hydrogen
H–H	74	436
H–O	96	366
H–F	92	568
H–Cl	127	432
C — Carbon
C–H	109	413
C–C	154	348
C=C	134	614
C≡C	120	839
C–N	147	308
C–O	143	360
C–F	134	488
C–Cl	177	330
N — Nitrogen
N–H	101	391
N–N	145	170
N≡N	110	945
O — Oxygen
O–O	148	145
O=O	121	498
F, Cl, Br, I — Halogens
F–F	142	158
Cl–Cl	199	243
Br–H	141	366
Br–Br	228	193
I–H	161	298
I–I	267	151

Strong chemical bonds are the intramolecular forces which hold atoms together in molecules. A strong chemical bond is formed from the transfer or sharing of electrons between atomic centers and relies on the electrostatic attraction between the protons in nuclei and the electrons in the orbitals. Although these bonds typically involve the transfer of integer numbers of electrons (this is the bond order), some systems can have intermediate numbers. An example of this is the organic molecule benzene, where the bond order is 1.5 for each carbon molecule.

The types of strong bond differ due to the difference in electronegativity of the constituent elements. A large difference in electronegativity leads to more polar (ionic) character in the bond.

Covalent bond

Covalent bonding is a common type of bonding, in which the electronegativity difference between the bonded atoms is small or nonexistent. Bonds within most organic compounds are described as covalent. See sigma bonds and pi bonds for LCAO-description of such bonding.

A polar covalent bond is a covalent bond with a significant ionic character. This means that the electrons are closer to one of the atoms than the other, creating an imbalance of charge. They occur as a bond between two atoms with moderately different electronegativities, and give rise to dipole-dipole interactions.

A coordinate covalent bond is one where both bonding electrons are from one of the atoms involved in the bond. These bonds give rise to Lewis acids and bases. The electrons are shared roughly equally between the atoms in contrast to ionic bonding. Such bonding occurs in molecules such as the ammonium ion (NH₄⁺) and are shown by an arrow pointing to the Lewis acid.

Ionic bond

Ionic bonding is a type of electrostatic interaction between atoms which have a large electronegativity difference. There is no precise value that distinguishes ionic from covalent bonding but a difference of electronegativity of over 1.7 is likely to be ionic and a difference of less than 1.7 is likely to be covalent.^[5] Ionic bonding leads to separate positive and negative ions, by the positive (cationic) atom donating a electron to the negative (anionic) atom. Ionic charges are commonly between −3e to +3e. Ionic bonding commonly occurs in metal salts such as sodium chloride (table salt).

One- and three-electron bonds

Bonds with one or three electrons can be found in radical species, which have an odd number of electrons. The simplest example of a 1-electron bond is found in the hydrogen molecular cation, H₂⁺. One-electron bonds often have about half the bond energy of a 2-electron bond, and are therefore called "half bonds". However, there are exceptions: in the case of dilithium, the bond is actually stronger for the 1-electron Li₂⁺ than for the 2-electron Li₂. This exception can be explained in terms of hybridization and inner-shell effects. ^[6]

The simplest example of three-electron bonding can be found in the helium dimer cation, He₂⁺, and can also be considered a "half bond" because, in molecular orbital terms, the third electron is in an anti-bonding orbital which cancels out half of the bond formed by the other two electrons. Another example of a molecule containing a 3-electron bond, in addition to two 2-electron bonds, is nitric oxide, NO. The oxygen molecule, O₂ can also be regarded as having two 3-electron bonds and one 2-electron bond, which accounts for its paramagnetism and its formal bond order of 2.^[7]

Molecules with odd-electron bonds are usually highly reactive. These types of bond are only stable between atoms with similar electronegativities.^[7]

Bent bonds

Bent bonds, also known as banana bonds, are bonds in strained or otherwise sterically hindered molecules whose binding orbitals are forced into a banana-like form. Bent bonds are often more susceptible to reactions than ordinary bonds.

3c-2e and 3c-4e bonds

In three-center two-electron bonds ("3c-2e") three atoms share two electrons in bonding. This type of bonding occurs in electron deficient compounds like diborane. Each such bond (2 per molecule in diborane) contains a pair of electrons which connect the boron atoms to each other in a banana shape, with a proton (nucleus of a hydrogen atom) in the middle of the bond, sharing electrons with both boron atoms.

Three-center four-electron bonds ("3c-4e") also exist which explain the bonding in hypervalent molecules. In certain cluster compounds, so-called four-center two-electron bonds also have been postulated.

In certain conjugated π (pi) systems, such as benzene and other aromatic compounds (see below), and in conjugated network solids such as graphite, the electrons in the conjugated system of π-bonds are spread over as many nuclear centers as exist in the molecule or the network.

Aromatic bond

In organic chemistry, certain configurations of electrons and orbitals infer extra stability to a molecule. This occurs when π orbitals overlap and combine with others on different atomic centres, forming a long range bond. For a molecule to be aromatic, it must obey Hückel's rule, where the number of π electrons fit the formula 4n + 2, where n is an integer. The bonds involved in the aromaticity are all planar.

In benzene, the prototypical aromatic compound, 18 (n = 4) bonding electrons bind 6 carbon atoms together to form a planar ring structure. The bond "order" (average number of bonds) between the different carbon atoms may be said to be (18/6)/2=1.5, but in this case the bonds are all identical from the chemical point of view. They may sometimes be written as single bonds alternating with double bonds, but the view of all ring bonds as being equivalently about 1.5 bonds in strength, is much closer to truth.

In the case of heterocyclic aromatics and substituted benzenes, the electronegativity differences between different parts of the ring may dominate the chemical behaviour of aromatic ring bonds, which otherwise are equivalent.

Metallic bond

In a metallic bond, bonding electrons are delocalized over a lattice of atoms. By contrast, in ionic compounds, the locations of the binding electrons and their charges are static. Because of delocalization or the free moving of electrons, it leads to the metallic properties such as conductivity, ductility and hardness.

Intermolecular bonding

There are four basic types of bonds that can be formed between two or more (otherwise non-associated) molecules, ions or atoms. Intermolecular forces cause molecules to be attracted or repulsed by each other. Often, these define some of the physical characteristics (such as the melting point) of a substance.

A large difference in electronegativity between two bonded atoms will cause dipole-dipole interactions. The bonding electrons will, on the whole, be closer to the more electronegative atom more frequently than the less electronegative one, giving rise to partial charges on each atomic center, and causing electrostatic forces between molecules.

A hydrogen bond is effectively a strong example of a permanent dipole. The large difference in electronegativities between hydrogen and any of fluorine, nitrogen and oxygen, coupled with their lone pairs of electrons cause strong electrostatic forces between molecules. Hydrogen bonds are responsible for the high boiling points of water and ammonia with respect to their heavier analogues.

The London dispersion force arises due to instantaneous dipoles in neighbouring atoms. As the negative charge of the electron is not uniform around the whole atom, there is always a charge imbalance. This small charge will induce a corresponding dipole in a nearby molecule; causing an attraction between the two. The electron then moves to another part of the electron cloud and the attraction is broken.

A cation-pi interaction occurs between the negative charges of pi bonds above and below an aromatic ring and a cation.

Electrons in chemical bonds

In the (unrealistic) limit of "pure" ionic bonding, electrons are perfectly localized on one of the two atoms in the bond. Such bonds can be understood by classical physics. The forces between the atoms are characterized by isotropic continuum electrostatic potentials. Their magnitude is in simple proportion to the charge difference.

Covalent bonds are better understood by valence bond theory or molecular orbital theory. The properties of the atoms involved can be understood using concepts such as oxidation number. The electron density within a bond is not assigned to individual atoms, but is instead delocalized between atoms. In valence bond theory, the two electrons on the two atoms are coupled together with the bond strength depending on the overlap between them. In molecular orbital theory, the linear combination of atomic orbitals (LCAO) helps describe the delocalized molecular orbital structures and energies based on the atomic orbitals of the atoms they came from. Unlike pure ionic bonds, covalent bonds may have directed anisotropic properties. These may have their own names, such as Sigma and Pi bond.

In the general case, atoms form bonds that are intermediates between ionic and covalent, depending on the relative electronegativity of the atoms involved. This type of bond is sometimes called polar covalent.

References

^ Campbell, Neil A. (2006). Biology: Exploring Life. Boston, Massachusetts: Pearson Prentice Hall. ISBN 0-13-250882-6. {{cite book}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
^ Lewis, Gilbert N. (1916). "The Atom and the Molecule". Journal of the American Chemical Society. 38 (4): 772. doi:10.1021/ja02261a002.
^ Laidler, K. J. (1993) The World of Physical Chemistry, Oxford University Press, p. 347
^ James, Hubert M.; Coolidge, Albert Sprague (1933). "The Ground State of the Hydrogen Molecule". Journal of Chemical Physics. 1 (12). American Institute of Physics: 825–835. doi:10.1063/1.1749252.
^ Atkins, Peter (1997). Chemistry: Molecules, Matter and Change. New York: W. H. Freeman & Co. pp. 294–295. ISBN 0-7167-3107-X. {{cite book}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
^ Weinhold, F.; Landis, C. Valency and bonding, Cambridge, 2005; pp. 96-100.
^ ^a ^b Pauling, L. The Nature of the Chemical Bond. Cornell University Press, 1960.

External links

UC Berkeley Chemistry lecture on chemical bonds
W. Locke (1997). Introduction to Molecular Orbital Theory. Retrieved May 18, 2005.
Carl R. Nave (2005). HyperPhysics. Retrieved May 18, 2005.
Linus Pauling and the Nature of the Chemical Bond: A Documentary History. Retrieved February 29, 2008.

[1] Campbell, Neil A. (2006). Biology: Exploring Life. Boston, Massachusetts: Pearson Prentice Hall. ISBN 0-13-250882-6. {{cite book}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)

[2] Lewis, Gilbert N. (1916). "The Atom and the Molecule". Journal of the American Chemical Society. 38 (4): 772. doi:10.1021/ja02261a002.

[3] Laidler, K. J. (1993) The World of Physical Chemistry, Oxford University Press, p. 347

[4] James, Hubert M.; Coolidge, Albert Sprague (1933). "The Ground State of the Hydrogen Molecule". Journal of Chemical Physics. 1 (12). American Institute of Physics: 825–835. doi:10.1063/1.1749252.

[5] Atkins, Peter (1997). Chemistry: Molecules, Matter and Change. New York: W. H. Freeman & Co. pp. 294–295. ISBN 0-7167-3107-X. {{cite book}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)

[6] Weinhold, F.; Landis, C. Valency and bonding, Cambridge, 2005; pp. 96-100.

[pauling-7] Pauling, L. The Nature of the Chemical Bond. Cornell University Press, 1960.

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