Hybrid Atomic Orbitals


By the end of this section, you will be able to:

  • Explain the concept of atomic orbital hybridization
  • Determine the hybrid orbitals associated with various molecular geometries

Thinking in terms of overlapping atomic orbitals is one way for us to explain how chemical bonds form in diatomic molecules. However, to understand how molecules with more than two atoms form stable bonds, we require a more detailed model. As an example, let us consider the water molecule, in which we have one oxygen atom bonding to two hydrogen atoms. Oxygen has the electron configuration 1s22s22p4, with two unpaired electrons (one in each of the two 2p orbitals). Valence bond theory would predict that the two O–H bonds form from the overlap of these two 2p orbitals with the 1s orbitals of the hydrogen atoms. If this were the case, the bond angle would be 90°, as shown in Figure 1 below, because p orbitals are perpendicular to each other. Experimental evidence shows that the bond angle is 104.5°, not 90°. The prediction of the valence bond theory model does not match the real-world observations of a water molecule; a different model is needed.

The hypothetical overlap of two of the 2p orbitals on an oxygen atom (red) with the 1s orbitals of two hydrogen atoms (blue) would produce a bond angle of 90°. This is not consistent with experimental evidence.1

Quantum-mechanical calculations suggest why the observed bond angles in H2O differ from those predicted by the overlap of the 1s orbital of the hydrogen atoms with the 2p orbitals of the oxygen atom. The mathematical expression known as the wave function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes. This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the linear combination of atomic orbitals, LCAO, (a technique that we will encounter again later). The new orbitals that result are called hybrid orbitals. The valence orbitals in an isolated oxygen atom are a 2s orbital and three 2p orbitals. The valence orbitals in an oxygen atom in a water molecule differ; they consist of four equivalent hybrid orbitals that point approximately toward the corners of a tetrahedron ((a), below). Consequently, the overlap of the O and H orbitals should result in a tetrahedral bond angle (109.5°). The observed angle of 104.5° (b, below) is experimental evidence for which quantum-mechanical calculations give a useful explanation: Valence bond theory must include a hybridization component to give accurate predictions.

(a) A water molecule has four regions of electron density, so VSEPR theory predicts a tetrahedral arrangement of hybrid orbitals. (b) Two of the hybrid orbitals on oxygen contain lone pairs, and the other two overlap with the 1s orbitals of hydrogen atoms to form the O–H bonds in H2O. This description is more consistent with the experimental structure.

The following ideas are important in understanding hybridization:

  1. Hybrid orbitals do not exist in isolated atoms. They are formed only in covalently bonded atoms.
  2. Hybrid orbitals have shapes and orientations that are very different from those of the atomic orbitals in isolated atoms.
  3. A set of hybrid orbitals is generated by combining atomic orbitals. The number of hybrid orbitals in a set is equal to the number of atomic orbitals that were combined to produce the set.
  4. All orbitals in a set of hybrid orbitals are equivalent in shape and energy.
  5. The type of hybrid orbitals formed in a bonded atom depends on its electron-pair geometry as predicted by the VSEPR theory.
  6. Hybrid orbitals overlap to form σ bonds. Unhybridized orbitals overlap to form π bonds.

In the following sections, we shall discuss the common types of hybrid orbitals.