Bonding Types

Given the electronic configurations of any element or ion, it is possible to determine the combination of orbitals and suborbitals used in forming chemical bonds. This can be done on two levels: (a) the valence bond atomic orbital method; and, (b) the molecular orbital method. The former is used for descriptions of VSEPR geometry of simple covalent inorganic molecules; the latter is used for descriptions of geometry in simple covalent organic molecules. These two approaches can be combined to serve as more complete descriptors. There are no orbital descriptions for ionic molecules, whether inorganic or organic, because ionic bonds consist of electron transfer, not sharing, and are in principle existent only by virtue of Coulomb's Law of Electromagnetic Attraction: F = 1 q1q2 4 0 r2 F is the coulombic force of attraction or repulsion measured in Newtons, has its usual 2 meaning, 0 is the permittivity constant = 8.85 x 10-12 coulomb2/Newton-meter , q is the charge on the first ion in coulombs, q is the charge on the second ion in coulombs, and r is the distance between them in meters. Note: A charge of +1 or 1 on an ion equals 1.60 x 10-19 coulombs. A permittivity constant is a measure of the ability for electromagnetic attraction to pass through a particular medium, in this case air. It would have a different value for water, for example. Larger integer ionic charges multiply the coulombic charge accordingly. The first term is a constant, so the expression can be rewritten as: F = (8.99 x 109 newton-meter2/coulomb2) q1q2 r2 Valence Bond Atomic Orbitals Given the electronic configuration of any element, only electrons in the valence orbital, the outermost orbital, are involved in covalent bond formation. Valence orbitals include any empty or partially filled suborbitals in that orbital. This means that nonionic elements in the third or later period of the Periodic Table of Elements contain unfilled d or f suborbitals as part of their valence orbitals. Examples: 2 2 3 2 3 7N = 1s 2s 2p is complete electron configuration; 2s 2p is incompletely filled valence orbital
15P

= 1s22s22p63s23p33d0 is complete electron configuration; 3s23p33d0 is incompletely filled valence orbital

Note: Pictures of s, p, d, f suborbitals are provided in the Quantum Numbers review. Hybridization is the physical/mathematical process of mixing the energies of valence orbitals to make them all energetically equivalent. Since s suborbitals are lower energy, more stable, than p suborbitals, which are in turn lower energy than d suborbitals, there must be some benefit gained through hybridization that outweighs making some suborbitals less stable. This benefit arises from the uncoupling of paired electrons within a single suborbital. By separating electrons, by placing them in different energetically equivalent suborbitals, the Coulombic repulsive force between them is reduced.

When atoms form single bonds with other atoms, they hybridize all the completely or partially filled suborbitals. When atoms form double bonds with other atoms, they hybridize all but one of the completely or partially filled suborbitals. When atoms form triple bonds with other atoms, they hybridize all but two of the completely or partially filled suborbitals. The unhybridized suborbitals in double or triple bonds are always p suborbitals. Examples: 2 3 7N = 2s 2p gains no benefit through hybridization because all valence orbitals are already partially or completely filled. No uncoupling of paired electrons is possible. Although we write the hybridization of Nitrogen in NH3 as sp3, this is a fiction, and employed only to insert consistency in designations for the VSEPR theory approach.
15P

= 3s23p33d0 gains substantial benefit through hybridization because the empty d suborbitals permit the uncoupling of electrons in the 3s suborbital. This means Phosphorous hybridizes to a configuration of 3s13p33d1, which is more simply written as sp3d in VSEPR theory for molecules such as PCl5.

The valence bond atomic orbital description of bonding in molecules simply lists the contributions of suborbitals, hydridized or not, coming from each atom participating in covalent bond formation. Examples: (1) Each of the three NH bonds in NH3 is described as sp3s coming from sp3 hydbridized suborbitals for Nitrogen and unhybridized s suborbitals from the three Hydrogens. (2) Each of the five PCl bonds in PCl5 is described as sp3dp coming from sp3d hydbridized suborbitals for Phosphorous and unhybridized p suborbitals from the five Chlorines. Octet Rule violation for halogens (Cl, Br, I) when bonded to multiple oxygen atoms derives from the rehybridization of the halogen atoms by use of empty d suborbitals. Example: = 1s22s22p63s23p53d0 rehybridizes its valence suborbitals to 3s13p33d3 thus permitting formation of seven bonds to as many as four Oxygens for a total of 14 valence orbital electrons. The valence bond designation of HClO4 is ssp3 for the HO bond, sp3sp3d3 for the (H)OCl bond, and sp3d3sp2 for the three Cl=O bonds: O || HOCl=O || O Molecular Orbitals Molecular orbitals derive from the physical/mathematical mixing of atomic suborbitals involved in covalent bond formation. This mixing of atomic suborbitals always produces pairs of molecular orbitals, which are designated as bonding and antibonding orbitals. As the names imply, the filling of bonding orbitals with electrons is a favorable process for molecular stability, while the filling of antibonding orbitals with electrons is a molecule destabilizing process. For

17Cl

this reason, bonding orbitals are always filled before antibonding orbitals with the available electrons. There are three types of molecular orbitals: (a) sigma, (b) pi, and (c) nonbonding. Sigma bonding orbitals (): the most stable, lowest in energy, orbital; always the first formed between two atoms, and always possesses s suborbital atomic character ( means s) Pi bonding orbitals (): next most stable; always form the second and third bonds between two atoms, and always possess unhybridized p suborbital atomic character ( means p) Non-bonding orbitals (n): always consist of non-reactive lone pair electrons on such elements as N, O, P, S, and halogens Sigma antibonding orbitals (*): the least stable, highest in energy, orbital; is always the last filled between two atoms Pi antibonding orbitals (*): between non-bonding and sigma antibonding orbitals in energy Examples: CH4 has four sigma single bonds formed from one sp3 hybridized Carbon suborbitals and four s unhybridized Hydrogen suborbitals. The eight electrons fill all the bonding orbitals and leave all the antibonding orbitals empty.

___ ___ ___ ___ * \ / \ Carbon sp3 \ / \ / /

s 4 Hydrogen

C2H4 has four sigma single bonds formed from two sp2 hybridized Carbon suborbitals and four s unhybridized Hydrogen suborbitals. It also has a sigma bond formed from two sp2 hybridized Carbon suborbitals, and a pi bond formed from two p unhybridized carbon suborbitals. The twelve electrons fill all the bonding orbitals and leave all the antibonding orbitals empty. ___ ___ ___ ___ *C-H __ *C-C / \ / \ / __ *C-C \ / \ p 2 Carbon sp2 \ \ \ \ / C-C / / C-C C-H / s 4 Hydrogen

Molecular Orbitals