Chemistry 100

Chemistry 100

Simple MOs for 2p overlap Because p overlap has increased electron density between nuclei, it would be expected to be lower in energy than pi overlap. There is some p-s mixing that occurs which complicates matters.

The s orbital can mix with the p orbital with symmetry. 1 MO Diagrams for B2 Expected Actual

2 3 MO Diagram for N2 with p-s mixing 4 Summary of p-s mixing

There is electron density in the p orbital along a given axis which can overlap with the s orbital of the other atom. The overlap of electron densities results in electron-electron repulsions which raise the energy of the p bonding orbital.

With increased nuclear charge there is a greater energy difference between the s and p orbitals and this overlap decreases. 5 How do we know? B2 is paramagnetic. 6

MO Diagrams for B2 through F2 7 Example 14.6 in the text Bond order:2 Bond energy: (kJ/mol)

2.5 495 1.5 643 395 8 What about NO?

Odd number of electrons (like He2+, O2+ and O2). Heteronuclear diatomic. Paramagnetic.

9 MO for HF Overlap with H1s and F2p. Unequal sharing.

10 Combining Models Simplicity of localized electron model (VBT) with delocalization characteristics of the MO model. 11

Combining Models Simplicity of localized electron model (VBT) with delocalization characteristics of the MO model. 12 Electrons in a Box

E = n2h2/8mL2 E = (n 2 n 2)[h2/8mL2] 4.6 x 1019 J f i

nf = 6; ni = 5 L 12 = 1.2 x 10-9 m m = 9.10939 x 1031 kg h = 6.62608 x 1034 Js E = hc/ 4.3 x 107 m or about 420-440 nm 13

Hybridization vs. MO for Methane 14

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