Web Release Date: April 11,
Long-Range Lennard-Jones and Electrostatic Interactions in Interfaces: Application of the Isotropic Periodic Sum Method
Laboratory of Computational Biology, National Heart, Lung, and Blood Institute, National Institutes of Health, Bethesda, Maryland 20892
Received: December 20, 2006
In Final Form: February 16, 2007
Abstract:
Molecular dynamics (MD) simulations of heptane/vapor, hexadecane/vapor, water/vapor, hexadecane/water,
and dipalmitoylphosphatidylcholine (DPPC) bilayers and monolayers are analyzed to determine the accuracy
of treating long-range interactions in interfaces with the isotropic periodic sum (IPS) method. The method
and cutoff (rc) dependences of surface tensions, density profiles, water dipole orientation, and electrostatic
potential profiles are used as metrics. The water/vapor, heptane/vapor, and hexadecane/vapor interfaces are
accurately and efficiently calculated with 2D IPS (rc = 10 Å). It is demonstrated that 3D IPS is not practical
for any of the interfacial systems studied. However, the hybrid method PME/IPS [Particle Mesh Ewald for
electrostatics and 3D IPS for Lennard-Jones (LJ) interactions] provides an efficient way to include both types
of long-range forces in simulations of large liquid/vacuum and all liquid/liquid interfaces, including lipid
monolayers and bilayers. A previously published pressure-based long-range LJ correction yields results similar
to those of PME/IPS for liquid/liquid interfaces. The contributions to surface tension of LJ terms arising
from interactions beyond 10 Å range from 13 dyn/cm for the hexadecane/vapor interface to approximately 3
dyn/cm for hexadecane/water and DPPC bilayers and monolayers. Surface tensions of alkane/vapor, hexadecane/water, and DPPC monolayers based on the CHARMM lipid force fields agree very well with experiment,
whereas surface tensions of the TIP3P and TIP4P-Ew water models underestimate experiment by 16 and 11
dyn/cm, respectively. Dipole potential drops (
) are less sensitive to long-range LJ interactions than surface
tensions. However, for the DPPC bilayer (845 ± 3 mV proceeding from water to lipid) and water (547
± 2 mV for TIP4P-Ew and 521 ± 3 mV for TIP3P) overestimate experiment by factors of 3 and 5, respectively,
and represent expected deficiencies in nonpolarizable force fields.
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