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@ARTICLE{VanMaaren:151995,
author = {Van Maaren, P. J. and Hong, M. and Hub, J. S. and Costa, L.
T. and Van Der Spoel, D. and Caleman, C. and DESY},
title = {{F}orce field benchmark of organic liquids: density,
enthalpy of vaporization, heat capacities, surface tension,
isothermal compressibility, volumetric expansion
coefficient, and dielectric constant},
journal = {Journal of chemical theory and computation},
volume = {8},
issn = {1549-9618},
address = {Washington, DC},
publisher = {American Chemical Society (ACS)},
reportid = {PHPPUBDB-26572},
pages = {61},
year = {2012},
note = {(c) American Chemical Society. Open Access.},
abstract = {The chemical composition of small organic molecules is
often very similar to amino acid side chains or the bases in
nucleic acids, and hence there is no a priori reason why a
molecular mechanics force field could not describe both
organic liquids and biomolecules with a single parameter
set. Here, we devise a benchmark for force fields in order
to test the ability of existing force fields to reproduce
some key properties of organic liquids, namely, the density,
enthalpy of vaporization, the surface tension, the heat
capacity at constant volume and pressure, the isothermal
compressibility, the volumetric expansion coefficient, and
the static dielectric constant. Well over 1200 experimental
measurements were used for comparison to the simulations of
146 organic liquids. Novel polynomial interpolations of the
dielectric constant (32 molecules), heat capacity at
constant pressure (three molecules), and the isothermal
compressibility (53 molecules) as a function of the
temperature have been made, based on experimental data, in
order to be able to compare simulation results to them. To
compute the heat capacities, we applied the two phase
thermodynamics method (Lin et al. J. Chem. Phys.2003, 119,
11792), which allows one to compute thermodynamic properties
on the basis of the density of states as derived from the
velocity autocorrelation function. The method is implemented
in a new utility within the GROMACS molecular simulation
package, named $g_dos,$ and a detailed exposé of the
underlying equations is presented. The purpose of this work
is to establish the state of the art of two popular force
fields, OPLS/AA (all-atom optimized potential for liquid
simulation) and GAFF (generalized Amber force field), to
find common bottlenecks, i.e., particularly difficult
molecules, and to serve as a reference point for future
force field development. To make for a fair playing field,
all molecules were evaluated with the same parameter
settings, such as thermostats and barostats, treatment of
electrostatic interactions, and system size (1000
molecules). The densities and enthalpy of vaporization from
an independent data set based on simulations using the
CHARMM General Force Field (CGenFF) presented by
Vanommeslaeghe et al. (J. Comput. Chem.2010, 31, 671) are
included for comparison. We find that, overall, the OPLS/AA
force field performs somewhat better than GAFF, but there
are significant issues with reproduction of the surface
tension and dielectric constants for both force fields.},
cin = {FS-CFEL-1},
ddc = {540},
cid = {I:(DE-H253)FS-CFEL-1-20120731},
pnm = {Experiments at CFEL (POF2-544)},
pid = {G:(DE-H253)POF2-CFEL-Exp.-20130405},
experiment = {EXP:(DE-H253)CFEL-Exp-20150101},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:22241968},
pmc = {pmc:PMC3254193},
UT = {WOS:000298908500007},
doi = {10.1021/ct200731v},
url = {https://bib-pubdb1.desy.de/record/151995},
}