Molecular Orbital Theory. WX AP Chemistry Chapter 9 Adapted from: Luis Bonilla Abel Perez University of Texas at El Paso

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1 Molecular Orbital Theory WX AP Chemistry Chapter 9 Adapted from: Luis Bonilla Abel Perez University of Texas at El Paso

2 Molecular Orbital Theory The goal of molecular orbital theory is to describe molecules in a similar way to how we describe atoms, that is, in terms of orbitals, orbital diagrams, and electron configurations.

3 Forming a Covalent Bond Molecules can form bonds by sharing electron Two shared electrons form a single bond Atoms can share one, two or three pairs of electrons forming single, double and triple bonds Other types of bonds are formed by charged atoms (ionic) and metal atoms (metallic).

4 Atomic and Molecular Orbitals (cont d) Orbital Mixing When atoms share electrons to form a bond, their atomic orbitals mix to form molecular bonds. In order for these orbitals to mix they must: Have similar energy levels. Overlap well. Be close together. This is and example of orbital mixing. The two atoms share one electron each from there outer shell. In this case both 1s orbitals overlap and share their valence electrons. Overall energy potential lowers Video: Covalent Bonding PBS

5 Energy Diagram of Sigma Bond Formation by Orbital Overlap

6 Examples of Sigma Bond Formation

7 Atomic and Molecular Orbitals In atoms, electrons occupy atomic orbitals, but in molecules they occupy similar molecular orbitals which surround the molecule. The two 1s atomic orbitals combine to form two molecular orbitals, one bonding (s) and one antibonding (s*). This is an illustration of molecular orbital diagram of H 2. Notice that one electron from each atom is being shared to form a covalent bond. This is an example of orbital mixing.

8 Constructive Overlap Wave overlap can - add together (constructive)

9 Destructive Overlap Wave overlap can interfere and be destructive

10 Wave Overlap Can be constructive or destructive Think of a swing

11 Molecular Orbital Theory Each line in the diagram represents an orbital. The molecular orbital volume encompasses the whole molecule. The electrons fill the molecular orbitals of molecules like electrons fill atomic orbitals in atoms

12 Molecular Orbital Theory Electrons go into the lowest energy orbital available to form lowest potential energy for the molecule. The maximum number of electrons in each molecular orbital is two. (Pauli exclusion principle) One electron goes into orbitals of equal energy, with parallel spin, before they begin to pair up. (Hund's Rule.) Video of MO Theory Video of O 2 and N 2

13 Molecular Orbital Diagram (H 2 )

14 Molecular Orbitals of H 2 For H 2, there s not much difference, just add one more electron. Both electrons drop in energy when H 2 is formed so the bond energy is greater D(H 2 ) = 4.48 ev

15 sp-hybrid MOs sp-hybrids are formed by first adding (or subtracting) the 2p orbital to the 2s orbital. Since two atomic orbitals are combined in this way, two hybrid orbitals are obtained. Then the four sp-hybrids (2 on each atom) are combined to form a really good bonding orbital and a really bad bonding orbital, along with two antibonding orbitals + = great overlap, good bonding orbital hybridization lowers the energy of s 2s + = poor overlap, poor bonding orbital hybridization increases the energy of s 2p, so it lies above the p 2p orbital in B 2, C 2, and N 2

16 p-orbital bonding When the p orbitals are involved, you can get two different types of bonds: s bonds and p bonds. s orbitals have cylindrical symmetry about the molecular axis, no nodal planes containing the axis p orbitals have one nodal plane containing the axis s interaction of 2p orbitals: p interaction of 2p orbitals: Atom Atom A B Atom Atom A B In each orientation, the orbitals can approach so they overlap constructively to form bonding orbitals, or destructively to form antibonding orbitals. s 2p s 2p * p 2p p 2p *

17 MO Diagram for O 2

18 MO Diagram for N2

19 Molecular Orbital Diagram (HF)

20 Molecular Orbital Diagram (CH 4 ) So far, we have only look at molecules with two atoms. MO diagrams can also be used for larger molecules.

21 Molecular Orbital Diagram (H 2 O)

22 Conclusions Bonding electrons are localized between atoms (or are lone pairs). Atomic orbitals overlap to form bonds. Two electrons of opposite spin can occupy the overlapping orbitals. Bonding increases the probability of finding electrons in between atoms. It is also possible for atoms to form ionic and metallic bonds.

23 References

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