Valence Bond Theory versus Molecular Orbital Theory

Valence Bond Theory: Chemical bonds are formed when two nuclei share a pair of electrons between them. These bonds are considered combinations of overlapping one-electron atomic orbitals. The bond is strongest when the two electrons are confined to a region between the two nuclei. This type of bond is described as a localized bond. For example, in methane, CH4, each pair of electrons is considered to be confined to the region between the carbon nucleus and a hydrogen nucleus. One of the limitations of valence bond theory is that it assumes all bonds are localized bonds. As we will see, this is not a valid assumption.

Molecular Orbital Theory: A theory of chemical bonding based on quantum mechanics that states that a chemical bond is a combination of atomic orbitals that form molecular orbitals. Molecular orbitals are often delocalized over two or more atoms.

Molecular Orbital Theory (Section 10.5)

Molecular Orbital Theory a more sophisticated approach to chemical bonding than Lewis Structures and Valence Bond Theory. Why?

Paramagnetism of O2
The Lewis structure of O2 and Valence Bond theory both predict O2 will be diamagnetic (with no unpaired electrons) But experimentally, we know O2 is paramagnetic (it has unpaired electrons). It is attracted to a magnet.

http://demoroom.physics.ncsu.edu/multimedia/video/5G30.20.1.MOV

Molecular Orbital Theory Cont.

vIn atoms, atomic orbitals (AO) represent regions of space where there is a high probability of finding an electron. Atomic orbitals have discrete energies as well. vIn molecules, molecular orbitals (MO) are regions of space where there is a high probability of finding an electron. Unlike atomic orbitals, however, molecular orbitals are often delocalized over two or more atoms. 1. Each MO has a definite, discrete energy. 2. A maximum of two electrons may occupy any MO (and then only if they have opposite spins). 3. MOs are filled with electrons, lowest energy to highest energy, in accord with Hunds rule.

What do these Molecular Orbitals look like?

Bonding and Antibonding Molecular Orbitals (MOs)

Bonding Molecular Orbital MOs with electron density concentrated in the regions
between atoms. Bonding MOs have lower energy and greater stability than the atomic orbitals from which it was formed

Antibonding Molecular Orbital MOs with electron density concentrated in regions

other than between the atoms. Anitbonding MOs have higher energy and lower stability than the atomic orbitals from which it was formed

1s

*1s

Molecular Orbital Energy Diagrams and Bond Order

Bond Order (BO) refers to the number of bonds that exist between two atoms

BO = [# of e in bonding MOs # of e in antibonding MOs]

What is the bond order for H2? BO = (2 0) = 1 HH single bond

Molecular Orbital Energy Diagram Add More Electrons

Electron Configuration for a Li atom? Li: 1s 2 2s1 How many electrons are in Li2? Li + Li = 3 + 3 = 6 e What is the molecular orbital configuration for Li2? Li2: (1s)2(*1s)2(2s)2 What is the bond order for Li2? BO = (4 2) = 1 LiLi single bond

Molecular Orbital Energy Diagram Nitrogen (N2)

Electron Configuration for a N atom? N: 1s 2 2s2 2p3 N + N = 7 + 7 = 14 e

Number of electrons found in a N2 molecule?

*2p *2p 2p 2p *2s 2s *1s 1s

What is the molecular orbital configuration for N 2? N2: (1s)2(*1s)2(2s) 2(*2s)2(2p) 4(2p)2 What is the bond order for N2? BO = (10 4) = 3
1s 2s 2p

Diamagnetic no unpaired electrons

triple bond N N

Molecular Orbital Energy Diagram Dioxygen (O2)

Earlier, you saw that O2 was attracted to the poles of a magnet. This is because O2 is paramagnetic (it contains unpaired electrons). The Lewis structure and Valence Bond Theory both incorrectly predict that O2 is diamagnetic (it contains no unpaired electrons)!

What does Molecular Orbital Theory predict? 1) Electron Configuration for an O atom? O: 1s 2 2s2 2p4 2) Number of electrons found in an O2 molecule? O + O = 8 + 8 = 16 e

Molecular Orbital Energy Diagram Dioxygen (O2) *2p *2p 2p 2p *2s 2s *1s 1s
What is the molecular orbital configuration for O2? O2: (1s)2(*1s) 2(2s)2(*2s) 2(2p)2( 2p) 4(*2p) 2 What is the bond order for O2? BO = (10 6) = 2 double bond O=O Is O2 paramagnetic or diamagnetic? Paramagnetic

2p

2s

1s