  We derive a mean-field free energy for the phase behaviour of coupled bilayer
leaflets, which is implicated in cellular processes and important to the design
of artificial membranes. Our model accounts for amphiphile-level structural
features, particularly hydrophobic mismatch, which promotes antiregistration
(AR), in competition with the `direct' trans-midplane coupling usually studied,
promoting registration (R). We show that the phase diagram of coupled leaflets
allows multiple \textit{metastable} coexistences, then illustrate the kinetic
implications with a detailed study of a bilayer of equimolar overall
composition. For approximate parameters estimated to apply to phospholipids,
equilibrium coexistence is typically registered, but metastable antiregistered
phases can be kinetically favoured by hydrophobic mismatch. Thus a bilayer in
the spinodal region can require nucleation to equilibrate, in a novel
manifestation of Ostwald's `rule of stages'. Our results provide a framework
for understanding disparate existing observations, elucidating a subtle
competition of couplings, and a key role for phase transition kinetics in
bilayer phase behaviour.
