T. Stefan et R. Janoschek, How relevant are S = O and P = O double bonds for the description of the acid molecules H2SO3, H2SO4, and H3PO4, respectively?, J MOL MODEL, 6(2), 2000, pp. 282-288
The acid molecules H2SO3, H2SO4, and H3PO4 are usually drawn using "Lewis s
tructures" which exhibit the octet extension by 3d-orbitals on sulfur and p
hosphorus, respectively. Thus, S=O and P=O double bonds are assumed to be f
ormed. The natural d-orbital occupancies on S and P, however, were calculat
ed to be as low as 0.1 e, and therefore, an octet extension can hardly be e
xpected. After the natural bond orbitals (NBO) search procedure was forced
to attempt to form different Lewis structures of bonds and lone pairs, we d
efined the optimal Lewis structure, if a dominant structure exists at all,
by the maximum electronic charge in Lewis orbitals. Indeed, sulfur obeys th
e octet rule in the optimal zwitterionic Lewis structures and does not form
S=O double bonds. No dominant resonance structure could be found for H3PO4
where polarized PO pi-bond and zwitterionic PO bond structures exhibit sim
ilar weights.