Will any hybridized orbital be lower in energy than all unhybridized orbitals?

1 Answer
May 29, 2016

ORBITAL HYBRIDIZATION EXAMPLE

We know that for example, 2s2s orbitals are lower in energy than 2p2p orbitals.

So, when one 2s2s and three 2p2p orbitals hybridize, we get four sp^3sp3 orbitals (like in methane, ammonia, water, etc).

Each sp^3sp3 orbital has 25%25% ss character, and 75%75% pp character, and they are all identical to each other. Their energies are automatically similar to the pure orbitals that contributed to their hybridization.

Any pp orbital started with 100%100% pp character, and any ss orbital started with 100%100% ss character.

Hence, with 25%25% ss character, the contribution from the 2s2s orbital makes the sp^3sp3 orbitals more similar to the energy of a pure 2s2s orbital than they were when they were pure, which means they become lower in energy.

In fact, the hybridized orbitals become intermediate in energy between the lowest-energy pure orbital and the higher-energy pure orbitals.


HYBRIDIZATION IN GENERAL

Of course, that example doesn't prove it in general, but it does get the main idea across. So now, let's put it this way.

For any (l)(l+1)^m(l+2)^n(l+3)^o(l)(l+1)m(l+2)n(l+3)o hybrid orbital (where ll is the angular momentum quantum number; mm, nn, and oo are the number of (l+1)(l+1), (l+2)(l+2), or (l+3)(l+3) orbitals contributing to the hybridization, respectively; and m_"max" = 3mmax=3, n_"max" = 5nmax=5, and o_"max" = 7omax=7):

  • No matter what, there will be an orbital or two for a particular ll that is lowest in energy, whether it's an nsns orbital, an (n-1)d(n1)d orbital, or an (n-2)f(n2)f orbital, or whatever.
  • That lowest-energy pure orbital's contribution to the hybridized orbital makes the hybridized orbital more similar in energy to that lowest-energy orbital.

Therefore, the hybrid orbital will always be lower in energy than the highest-energy pure contributing orbital.