RATIONALIZATION OF THE DIELECTRIC PROPERTIES OF COMMON THREE-SITE WATER MODELS IN TERMS OF THEIR FORCE FIELD PARAMETERS

The dielectric properties (static dielectric constant e0, Debye relaxation time τD and distance dependent Kirkwood G-factor Gk(R)) of commonly used three-site water models (the “simple point charge” models SPC and SPC/E, as well as the “transferable intermolecular potentials with three point charges” TIP3P and its CHARMM modified variant TIP3Pmod) were evaluated from 2 ns molecular dynamics simulations using the Ewald summation method to compute the electrostatic interactions. The results for SPC (e0=65±5, τD=7.6±0.8 ps) and SPC/E (e0=68±6, τD=12.1±1.3 ps) are in good agreement with the literature; for TIP3P (TIP3Pmod) we obtained a dielectric constant e0=97±7 (97±6) and a Debye relaxation time τD=7.3±0.7 ps (6.9±0.6 ps). The surprisingly large differences in e0 were rationalized by an investigation of the relationship between the force field parameters and the dielectric properties. Based on simulations of hybrid SPC/TIP3P models, the HOH bond angle was identified as the determining factor of the dielect...

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