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By the end of this section, you will be able to:
  • Outline the basic quantum-mechanical approach to deriving molecular orbitals from atomic orbitals
  • Describe traits of bonding and antibonding molecular orbitals
  • Calculate bond orders based on molecular electron configurations
  • Write molecular electron configurations for first- and second-row diatomic molecules
  • Relate these electron configurations to the molecules’ stabilities and magnetic properties

For almost every covalent molecule that exists, we can now draw the Lewis structure, predict the electron-pair geometry, predict the molecular geometry, and come close to predicting bond angles. However, one of the most important molecules we know, the oxygen molecule O 2 , presents a problem with respect to its Lewis structure. We would write the following Lewis structure for O 2 :

A Lewis structure is shown. It is made up of two oxygen atoms, each with two lone pairs of electrons, bonded together with a double bond.

This electronic structure adheres to all the rules governing Lewis theory. There is an O=O double bond, and each oxygen atom has eight electrons around it. However, this picture is at odds with the magnetic behavior of oxygen. By itself, O 2 is not magnetic, but it is attracted to magnetic fields. Thus, when we pour liquid oxygen past a strong magnet, it collects between the poles of the magnet and defies gravity, as in [link] . Such attraction to a magnetic field is called paramagnetism    , and it arises in molecules that have unpaired electrons. And yet, the Lewis structure of O 2 indicates that all electrons are paired. How do we account for this discrepancy?

Magnetic susceptibility measures the force experienced by a substance in a magnetic field. When we compare the weight of a sample to the weight measured in a magnetic field ( [link] ), paramagnetic samples that are attracted to the magnet will appear heavier because of the force exerted by the magnetic field. We can calculate the number of unpaired electrons based on the increase in weight.

A diagram depicts a stand supporting two objects that are held in balance by a horizontal bar. On the right, the bar supports a dish that is holding two weights. On the left there is a line attached to a test tube labeled, “Sample tube.” The test tube has been lowered into the space labeled, “Magnetic field,” between two structures labeled, “Electromagnets.”
A Gouy balance compares the mass of a sample in the presence of a magnetic field with the mass with the electromagnet turned off to determine the number of unpaired electrons in a sample.

Experiments show that each O 2 molecule has two unpaired electrons. The Lewis-structure model does not predict the presence of these two unpaired electrons. Unlike oxygen, the apparent weight of most molecules decreases slightly in the presence of an inhomogeneous magnetic field. Materials in which all of the electrons are paired are diamagnetic and weakly repel a magnetic field. Paramagnetic and diamagnetic materials do not act as permanent magnets. Only in the presence of an applied magnetic field do they demonstrate attraction or repulsion.

Molecular orbital theory (MO theory) provides an explanation of chemical bonding that accounts for the paramagnetism of the oxygen molecule. It also explains the bonding in a number of other molecules, such as violations of the octet rule and more molecules with more complicated bonding (beyond the scope of this text) that are difficult to describe with Lewis structures. Additionally, it provides a model for describing the energies of electrons in a molecule and the probable location of these electrons. Unlike valence bond theory, which uses hybrid orbitals that are assigned to one specific atom, MO theory uses the combination of atomic orbitals to yield molecular orbitals that are delocalized over the entire molecule rather than being localized on its constituent atoms. MO theory also helps us understand why some substances are electrical conductors, others are semiconductors, and still others are insulators. [link] summarizes the main points of the two complementary bonding theories. Both theories provide different, useful ways of describing molecular structure.

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Source:  OpenStax, Chemistry. OpenStax CNX. May 20, 2015 Download for free at http://legacy.cnx.org/content/col11760/1.9
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