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Overlap and Bonding

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  1. Overlap and Bonding • We think of covalent bonds forming through the sharing of electrons by adjacent atoms. • In such an approach this can only occur when orbitals on the two atoms overlap.

  2. Overlap and Bonding • Increased overlap brings the electrons and nuclei closer together while simultaneously decreasing electron-electron repulsion. • However, if atoms get too close, the internuclear repulsion greatly raises the energy.

  3. Hybridization: Animation

  4. Hybrid Orbitals But it’s hard to imagine tetrahedral, trigonal bipyramidal, and other geometries arising from the atomic orbitals we recognize.

  5. Hybrid Orbitals • Consider beryllium: • In its ground electronic state, it would not be able to form bonds because it has no singly-occupied orbitals.

  6. Hybrid Orbitals But if it absorbs the small amount of energy needed to promote an electron from the 2s to the 2p orbital, it can form two bonds.

  7. Hybrid Orbitals • Mixing the s and p orbitals yields two degenerate orbitals that are hybrids of the two orbitals. • These sp hybrid orbitals have two lobes like a p orbital. • One of the lobes is larger and more rounded as is the s orbital.

  8. Hybrid Orbitals • These two degenerate orbitals would align themselves 180 from each other. • This is consistent with the observed geometry of beryllium compounds: linear.

  9. Hybrid Orbitals • With hybrid orbitals the orbital diagram for beryllium would look like this. • The sp orbitals are higher in energy than the 1s orbital but lower than the 2p.

  10. Hybrid Orbitals Using a similar model for boron leads to…

  11. Hybrid Orbitals …three degenerate sp2 orbitals.

  12. Hybrid Orbitals With carbon we get…

  13. Hybrid Orbitals …four degenerate sp3 orbitals.

  14. Hybrid Orbitals For geometries involving expanded octets on the central atom, we must use d orbitals in our hybrids. An Example: Phosphorous atom

  15. Hybrid OrbitalsCentral Atoms of Expanded Octets This leads to five degenerate sp3d orbitals… …or six degenerate sp3d2 orbitals.

  16. Hybrid Orbitals Once you know the electron-domain geometry, you know the hybridization state of the atom.

  17. Which kind of hybridization is about the central atom in PCl5? sp2 sp3 sp4 sp3d

  18. Correct Answer: sp2 sp3 sp4 sp3d The hybridization for PCl5 is sp3d, as shown to the right.