Uhh..hhuuhhuu. He said orbital Yeah!.... Yeah!

Molecular Orbital Theory

We have seen that the Valence Bond model is of great value in interpreting the structure and bonding of molecules. However, their are some problems with this model. For example:
It incorrectly assumes that electrons are localized, and so the concept of resonance must be added. It does not deal effectively with molecules containing unpaired electrons, free radicals. It gives no direct information about bond energies

Paramagnetism arises in molecules that have one or more unpaired electrons resulting in attractions to a magnetic field.

Molecular Orbital Theory

Mullikens approach to molecular bonding was to derive molecular orbitals Robert Mulliken (1896 1986) that are spread out, or Received the 1966 Nobel Prize for delocalized over the entire development of the Molecular Orbital theory. molecule. The atomic orbitals of the atoms in the molecule combine to form a set of orbitals that are the property of the molecule, and the electrons of the molecule are distributed within these orbitals.

Another failure of VB theory is that it fails to correctly describe the bonding in the O2 molecule. The O2 molecule is paramagnetic, which requires the presence of unpaired electrons. The Lewis structure, however would have all electrons paired. The Molecular Orbital approach will show us that the molecule actually has two unpaired electrons. (think about that!)

MO can be difficult to understand at times so we will take a step by step approach. In MO theory we begin with a given arrangement of atoms in the molecule at known bond distances. Initially, we disregard the presence of the valence electrons in the atoms and consider the overlap of empty valence orbitals to determine the sets of molecular orbitals. These molecular orbitals more or less encompass all the atoms of the molecule, and the valence electrons for all the atoms in the molecule are then assigned to the molecular orbitals.

First Principle of MO Theory

The total number of molecular orbitals is always equal to the total number of atomic orbitals contributed by the atoms that have combined.
In MO theory, we invoke the wave nature of electrons. The square of the molecular orbital wave function describes electron probability for molecules. Molecular orbitals can only hold two electrons.

Lets investigate H2

Molecular Orbitals
If waves interact constructively, the resulting orbital is lower in energy: a bonding molecular orbital. When the 1s orbitals of two hydrogen atoms overlap, two molecular orbitals form from the combination of the overlapping orbitals. The lower energy MO concentrates electron density between the nuclei labeled 1s indicating that 1s atomic orbitals were used to create a electron distribution. Because electrons in the bonding MO are localized between both nuclei, they are more stable (lower energy) than in their original atomic orbitals.

Molecular Orbitals
If waves interact destructively, the resulting orbital is higher in energy: an antibonding molecular orbital. The other MO that forms reduces the probability of finding the electrons between the nuclei and increases the probability of finding the electron in other regions. Without significant electron density between them, the nuclei repel each other. This antibonding MO, is also formed from the same 1s orbitals and is signified as antibonding by the addition of an asterisk, *1s. Electrons in this region are repelled from the bonding region and are therefore less stable than their original atomic positions.

Second Principle of MO Theory

The bonding molecular orbital is lower in energy than the parent orbitals, and the antibonding orbital is higher in energy.
This means that the energy of a group of atoms is lower than the energy of the separated atoms when electrons are assigned to bonding MOs. Molecules are stabilized by chemical bond formations in bonding MOs and destabilized when electrons are assigned to antibonding MOs because the energy of the molecule is higher than that of the atoms themselves.

MO for Hydrogen
In H2 the two electrons go into the bonding molecular orbital. Therefore, the electrons are more stable, or have lower energy than they did in their atomic orbitals. Molecular orbital diagrams are used to show energy relations between atomic orbitals and MOs. Here we see the obvious lower energy arrangement for 2 atoms of hydrogen in a covalent compound vs. existing as individual atoms.

Third Principle of MO Theory

Electrons of the molecule are assigned to orbitals of successively higher energy according to the Pauli exclusion principle and Hunds rule.
This is analogous to the procedure for filling atomic orbitals Thus, electrons occupy the lowest energy with paired spins. Because the paired electrons in the bonding MO of H2 are lower than that of either parent 1s electron, the H2 molecule is stable. H2 has an electron configuration of: H2 (1s )2

MO for Helium
In contrast, look at the MOs for two helium atoms that try to form a bond. 2 MOs, bonding and antibonding form from the 2 1s orbitals just like hydrogen. However, there are four electrons to distribute among the MOs. Two fit into the bonding and two into the antibonding The stabilizing effect of the 1s pair is canceled by the destabilizing effect of the *1s pair, so no bond forms.

Bond Order
The bond order is one half the difference between the number of bonding and antibonding electrons. For hydrogen, with two electrons in the bonding MO and none in the antibonding MO, the bond order is

MO for Helium
Here, a helium atom has lost an electron via a Redox reaction and the question is asked: could an ion of He2+ form? Notice, the first two electrons fill the bonding MO leaving one to be placed in the antibonding. The bond order works out to be +1/2. Therefore, the ion is more stable than the two atoms separately. What about He22+?

1 (2 - 0) = 1 2 1 (2 - 2) = 0 2 A bond order of 1 represents a single bond, 2 a double bond, 3 a triple bond, and 0 meaning no bonds form.
In the case of He2, the bond order would be

MO for Lithium
The MO diagram for lithium shows the 2 bonding and 2 antibonding orbitals formed from the 1s and 2s atomic orbitals to make a molecule of Li2. The bonding effect of the 1s electrons is canceled by the antibonding effect of the *1s electrons, so these pairs make no net contribution to bonding in Li2. Bonding in Li2 is due to the 2s electron pair assigned to the orbital, and the bond order is 1.

1. Write a MO diagram to determine if Beryllium should form a homonuclear diatomic molecule?

Fourth Principle of MO Theory

Atomic orbitals combine to form molecular orbitals most effectively when the atomic orbitals are of similar energy.
Since lithium has electrons in both the 1s and 2s, 1s 2s MOs are theoretically possible. Because the 1s and the 2s atomic orbitals are quite different in energy this interaction can be disregarded. When atomic orbitals of different energies are combined to form MOs Lets just say we would need a little more time than we have to study them.

MOs for p Orbitals

For atoms with both s and p orbitals, there are two types of interactions:
The s and the p orbitals that face each other overlap in fashion. The other two sets of p orbitals overlap in fashion.

The result is 2 pair of MOs and 2 pair of MOs each with different energy max and mins.

Energy Diagram for Second Row Homonuclear Diatomic Molecules

According to the energy of the p sublevel molecular orbitals, the resulting MO diagram looks like this. There are both and bonding molecular orbitals and * and * antibonding molecular orbitals.

2s - 2p Confusion I mean Interaction

The smaller p-block elements in the second period (B,C,N) have a sizeable interaction between the s and p orbitals. The interactions force the 2s energy lower and the 2p energy higher. This flips the order of the s and p molecular orbitals in these elements. Larger p-block elements are affected less by these interactions and the orbitals do not flip.

Homonuclear Diatomic Molecules B2 Through Ne2

Filling the energy-level diagram following the principles presented, produces the electron assignments seen on the next slide. Notice the correlation between the electron arrangement and the bond orders, bond lengths, and bond energies. Also, notice the configuration for dioxygen

Flipped 2p and 2

Paramagnetism vs. Dimagnetism

You should have noticed that the electron arrangement of oxygen according to MO has two unpaired electrons and two bonds.

Not Flipped

C, N, F and Ne are all diamagnetic

Heteronuclear Diatomic Molecules

Remember NO? A Free radical with an odd number of electrons. According to VB, it should not exist. MO can explain how the NO molecule is both stable and paramagnetic as well as highly reactive. The MO energy diagram must account for the different energies of the atomic orbitals of both nitrogen and oxygen when forming MOs. IN heteronuclear MOs, the atomic energies of the more electronegative atom will be lower in energy than those of the less electronegative element.

Here we see the MOs for the bonding orbitals are shifted toward the more electronegative O atom and the antibonding orbitals are shifted toward the less electronegative atom. The bond order is then seen as 2.5 and since the odd electron is in the *2p MOs that are more closely associated with N, the lewis structure with no formal charges should be preferred. (check and see)

MO and Resonance
From the energy-level diagram for 2nd period atoms, it should be easy to see how delocalized electrons could be accounted for in molecules exhibiting resonance according to VB theory Not only are electrons accounted for but according to MO theory the molecular orbitals containing these electrons are distributed over the entire molecule themselves which was a problem for VB.

Therefore, for benzene, we should see electrons on the internuclear axis

And, since there are electrons, they should be distributed over the entire molecule (MO)

Energy Absorption
Ever ask the question how do electrons move to excited states in H2?
For atoms, it is simple: They jump from one atomic orbital to another. What about molecules where the electrons should be localized between the nuclei (VB)? Not a problem with MO. Electrons can move to antibonding MOs then release their photons as they return to their ground state bonding MOs. Neat Huh?