This observation may be generalized for any hydrogen bonding of the type X-HY

where XH replaces HF and Y replace F-. If the HOMO of Y and the LUMO of HX have
comparable energies, both occupied orbitals in X-HY will be lower than either of the
interacting orbitals. Consequently the hydrogen bonded unit X-HY will have a lower
total energy compared to X-H and Y in a 3-centre-4-electron MO system.

If X is highly electronegative element, its highest occupied orbital will lie much lower in
energy than the 1s orbital of H and H-X bond will be polar with major electron density
near X. This will favour hydrogen bonding with Y whereby the energy of the bonding
MO of HX will be further lowered.
If the energy of the HOMO of Y lies far below that of the LUMO of XH, the HOMO in
XHY will be above the Y-orbital and will not serve to stabilize the system. A still
greater mismatch in the energies of HOMO and LUMO will stabilize the system in
favour of YH+ and X- by transfer of a hydrogen (proton). We shall find more application
of such HOMO-LUMO interaction in connection with acids and bases.

It is not difficult to understand why other atoms cannot form bonds similar to
hydrogen bonds. For greatest interaction, either electrostatic or covalent, the
participating atoms should approach as close as possible. Hydrogen has two
favourable points in this respect: (i) its small size and (ii) absence of inner electron
shells. This is why in a hydrogen bond X-HY, X and Y can approach very close to each
other without involving large repulsion. Replacement of H by a larger atom, say
Na(3s1), would cause enough repulsion from the inner shell of electrons to offset the
net binding.

The hydrogen bond differs from the

hydrogen bridge bond involved in
explaining the bonding in B2H6 and other
boranes (see text). The B-H-B hydrogen
bridge bond involves a 3-centre-2-electron
(3e-2e) system.