A highly accurate aniostropic intermolecular potential for diatomic hydrogen has been developed that is transferable for molecular modeling in heterogeneous systems. The potential surface is designed to be efficacious in modeling mixed sorbates in metal-organic materials that include sorption interactions with charged interfaces and open metal sites. The potential parameters are compatible for mixed simulations but still maintain high accuracy while deriving dispersion parameters from a proven polarizability model. The potential includes essential physical interactions including: short-range repulsions, dispersion, and permanent and induced electrostatics. Many-body polarization is introduced via a point-atomic polarizability model that is also extended to account for many-body van der Waals interactions in a consistent fashion. Permanent electrostatics are incorporated using point partial charges on atomic sites. However, contrary to expectation, the best potentials are obtained by permitting the charges to take on values that do not reproduce the first non-vanishing moment of the electrostatic potential surface, i.e., the quadrupole moment. Potential parameters are fit to match ab initio energies for a representative range of dimer geometries. The resulting potential is shown to be highly effective by comparing to electronic structure calculations for a thermal distribution of trimer geometries, and by reproducing experimental bulk pressure-density isotherms. The surface is shown to be superior to other similarly portable potential choices even in tests on homogeneous systems without strong polarizing fields. The present streamlined approach to developing such potentials allows for a simple adaptation to other molecules amenable to investigation by high-level electronic structure methods.
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21 May 2012
Research Article|
May 17 2012
A molecular H2 potential for heterogeneous simulations including polarization and many-body van der Waals interactions
Keith McLaughlin;
Keith McLaughlin
a)
1Department of Chemistry,
University of South Florida
, 4202 E. Fowler Ave., CHE205, Tampa, Florida 33620, USA
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Christian R. Cioce;
Christian R. Cioce
1Department of Chemistry,
University of South Florida
, 4202 E. Fowler Ave., CHE205, Tampa, Florida 33620, USA
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Jonathan L. Belof;
Jonathan L. Belof
2
Lawrence Livermore National Laboratory
, 7000 East Avenue, Livermore, California 94550, USA
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Brian Space
Brian Space
1Department of Chemistry,
University of South Florida
, 4202 E. Fowler Ave., CHE205, Tampa, Florida 33620, USA
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a)
Electronic mail: kmclaugh@physics.cas.usf.edu.
J. Chem. Phys. 136, 194302 (2012)
Article history
Received:
February 03 2012
Accepted:
April 28 2012
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Citation
Keith McLaughlin, Christian R. Cioce, Jonathan L. Belof, Brian Space; A molecular H2 potential for heterogeneous simulations including polarization and many-body van der Waals interactions. J. Chem. Phys. 21 May 2012; 136 (19): 194302. https://doi.org/10.1063/1.4717705
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