We
have used all-atom molecular dynamics (MD) simulations to calculate
the surface tension of melt poly(methyl methacrylate) (PMMA) as a
function of tacticity. Computation of surface tension using the Kirkwood-Buff
approach required hundreds of nanoseconds of equilibration. The computed
slopes of surface tension versus temperature are in very good agreement
with reported experimental values. Using a rigorous treatment of the
true interface, which takes into account the molecular roughness,
we find that isotactic PMMA, in comparison to syndiotactic and atactic
PMMA, shows a larger surface concentration of polar ester-methyl and
carbonyl groups on the surface versus nonpolar α-methyl groups.
A mechanistic hypothesis based on the helical nature of the isotactic
PMMA chains, their relative flexibility, and their reported conformational
energies is proposed to explain the trends in composition near the
surface. We highlight here how surface composition and surface tension
are controlled by both polarity and steric constraints imposed by
tacticity.