  Molecular dynamics simulations are utilized to study the melting transition
in pentane (C5H12) and heptane (C7H16), physisorbed onto the basal plane of
graphite at near-monolayer coverages. Through use of the newest, optimized
version of the anisotropic united-atom model (AUA4) to simulate both systems at
two separate coverages, this study provides evidence that the melting
transition for pentane and heptane monolayers are significantly different.
Specifically, this study proposes a very rapid transition from the solid
crystalline rectangular-centered (RC) phase to a fluid phase in pentane
monolayers, whereas heptane monolayers exhibit a slower transition that
involves a more gradual loss of RC order in the solid-fluid phase transition.
Through a study of the melting behavior, encompassing variations where the
formation of gauche defects in the alkyl chains are eliminated, this study
proposes that this gradual melting behavior for heptane monolayers is a result
of less orientational mobility of the heptane molecules in the solid RC phase,
as compared to the pentane molecules. This idea is supported through a study of
a nonane monolayer, which gives the gradual melting signature that heptane
monolayers also seem to indicate. The results of this work are compared to
previous experiment over pentane and heptane monolayers, and are found to be in
good agreement.
