We perform molecular
dynamics (MD) simulations of water capillary
bridges formed between parallel walls. The underlying structure of
the walls corresponds to hydroxilated (crystalline) β-cristobalite,
modified to cover a wide range of hydrophobicity/hydrophilicity. The
capillary bridges are stretched during the MD simulations, from wall–wall
separation h = 5 nm up to h ≈
7.5 nm, until they become unstable and break. During the stretching
process, we calculate the profiles of capillary bridges as well as
the force and pressure induced on the walls, among other properties.
We find that, for all walls separations and surface hydrophobicity/hydrophilicity
considered, the results from MD simulations are in excellent agreement
with the predictions from capillarity theory (CT). In addition, we
find that CT is able to predict very closely the limit of stability
of the capillary bridges, i.e., the value of h at
which the bridges break. We also confirm that CT predicts correctly
the relationship between the surface hydrophobicity/hydrophilicity
and the resulting droplets of the capillary bridge rupture. Depending
on the contact angle of water with the corresponding surface, the
rupture of the capillary bridges results in (i) a single droplet attached
to one of the walls, (ii) two identical, or (iii) two different droplets,
one attached to each wall. This work expands upon a previous study
of nanoscale droplets and (stable) capillary bridges where CT was
validated at the nanoscale using MD simulations. The validation of
CT at such small scales is remarkable, since CT is a macroscopic theory
that is expected to fail at <10 nm scales, where molecular details
may become relevant. In particular, we find that CT works for capillary
bridges that are ≈2-nm thick, comparable to the thickness of
the water–vapor interface.