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Ammonia

This species is postulated as an intermediate in some reactions. It is the simplest triatomic molecule. In it 2 electrons hold the molecule together. This is an example of a three center two electron bond.

Each H atom has only a 1s orbital, so to obtain MOs for the H3+ cation, we must make linear combinations of the three 1s orbitals. Since the terminal H atoms are symmetry related and must be considered as a pair, we must make Symmetry Adapted Linear Combinations (SALCs) of their orbitals to interact with the central atom: 1.) 2.)

This is the approach that we must use for all polyatomic molecules.

0 nodes so most stabile.

1 node so less stabile than 1.

The 1s orbital of H(B) does not have appropriate symmetry to interact with the combination of 1s(A) - 1s(C).

2 nodes

the least stabile.

Correlation diagram / Walsh diagrams

odnosno:

odnosno:

odnosno: The doubly-degenerate pair of MOs have e symmetry. Although they do not look alike, each orbital in the pair has the same energy. Notice that the orbitals have roughly the same symmetry as would px and py orbitals in the middle of the H3 ring.

There are three SALCs, one with a1 symmetry and two (considered together) with e symmetry.

s and pz have a1 symmetry and px and py (as a pair) possess e symmetry. C3

Combining MO of ammonia:

1s N orbital has the lowest energy, so it will belong mostly to N and will be 0a1 nonbonding MO.

2s N (a1) with a1 SALC gives 1a1 lowest energy bonding MO.

2pz N (a1) added with a1 SALC gives 2a1 bonding MO (actually nonbonding due to low overlap.)

2pz N (a1) subtrackted with a1 SALC gives 3a1 highest energy antibonding MO.

A combination of N 2px and 2py orbitals and linear combinations of 3 H1s orbitals have e symmetry

Two bonding e symetry low energy orbitals 2x 1e

Two antibonding e symetry high energy orbitals 2x 2e

MO diagram in Figure a1 symmetry orbitals Bondings, nonbonding, and antibonding MO e symmetry orbitals These are doubly degenerate orbitals which means that there is a pair at low energies and a pair at high energies (the same energy).

Properties of ammonia:

In NH3, the HOMO (Highly Occupied Molecular Orbital) is a mostly nitrogen based orbital that corresponds to the Lone pair of electrons. This is why ammonia acts as a Lewis base at the N atom. The LUMO (Lowest Unoccupied Molecular Orbital) is the 2e level that has more H character this shows why NH3 can also act as a Lewis acid through the H atoms.