The Dielectric Constant of cis- and trans-Decahydronaphthalene and Cyclohexane as a Function of Temperature and Frequency

Staudhammer, Peter; Seyer, Wm. F.

doi:10.1021/ja01557a006

Cited by 3 publications

(1 citation statement)

References 2 publications

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“…A reaction-field correction , was applied to account for the mean effect of electrostatic interactions beyond the long-range cutoff distance. The corresponding relative dielectric permittivities were set to 61 for the aqueous systems (as appropriate for the SPC model), to 6 for the simulations in cyclohexane (the same value as used in ref , which is somewhat higher than the experimental value of 2.05 to avoid cutoff artifacts), to 4.7 for the simulations in chloroform (based on the experimental value), or to the experimental permittivity ε (Table ) for the pure-liquid simulations of the 57 organic molecules. The reaction-field self-term and excluded-atom-term contributions to the energy, forces, and virial were included as described in ref .…”

Section: Computational Detailsmentioning

confidence: 99%

A GROMOS-Compatible Force Field for Small Organic Molecules in the Condensed Phase: The 2016H66 Parameter Set

Horta

Merz

Fuchs

et al. 2016

J. Chem. Theory Comput.

147

287

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This article reports on the calibration and validation of a new GROMOS-compatible parameter set 2016H66 for small organic molecules in the condensed phase. The calibration is based on 62 organic molecules spanning the chemical functions alcohol, ether, aldehyde, ketone, carboxylic acid, ester, amine, amide, thiol, sulfide, and disulfide, as well as aromatic compounds and nucleic-acid bases. For 57 organic compounds, the calibration targets are the experimental pure-liquid density ρliq and the vaporization enthalpy ΔHvap, as well as the hydration free energy ΔGwat and the solvation free energy ΔGche in cyclohexane, at atmospheric pressure and at (or close to) room temperature. The final root-mean-square deviations (RMSD) for these four quantities over the set of compounds are 32.4 kg m(-3), 3.5 kJ mol(-1), 4.1 kJ mol(-1), and 2.1 kJ mol(-1), respectively, and the corresponding average deviations (AVED) are 1.0 kg m(-3), 0.2 kJ mol(-1), 2.6 kJ mol(-1), and 1.0 kJ mol(-1), respectively. For the five nucleic-acid bases, the parametrization is performed by transferring the final 2016H66 parameters from analogous organic compounds followed by a slight readjustment of the charges to reproduce the experimental water-to-chloroform transfer free energies ΔGtrn. The final RMSD for this quantity over the five bases is 1.7 kJ mol(-1), and the corresponding AVED is 0.8 kJ mol(-1). As an initial validation of the 2016H66 set, seven additional thermodynamic, transport, and dielectric properties are calculated for the 57 organic compounds in the liquid phase. The agreement with experiment in terms of these additional properties is found to be reasonable, with significant deviations typically affecting either a specific chemical function or a specific molecule. This suggests that in most cases, a classical force-field description along with a careful parametrization against ρliq, ΔHvap, ΔGwat, and ΔGche results in a model that appropriately describes the liquid in terms of a wide spectrum of its physical properties.

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Section: Computational Detailsmentioning

confidence: 99%

A GROMOS-Compatible Force Field for Small Organic Molecules in the Condensed Phase: The 2016H66 Parameter Set

Horta

Merz

Fuchs

et al. 2016

J. Chem. Theory Comput.

147

287

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Direct measurement of electrostatic interactions between poly(methyl methacrylate) microspheres with optical laser tweezers

et al. 2019

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Excluded-Volume Effects in Dilute Polymer Solutions. I. Equilibrium Properties

Norisuye

Kawahara

Teŕamoto

et al. 1968

The Journal of Chemical Physics

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Data of the statistical radius (S2 )112 and the second virial coefficient A2 were obtained for sharp fractions of polychloroprene (PCP) in methyl ethyl ketone (MEK), n-butyl acetate, and carbon tetrachloride at 25°C and in trans-decalin at temperatures ranging from 1 ° to 50°C. MEK at 25°C and trans-decalin at 2°C were found to be theta solvents for PCP. From these data two dimensionless quantities defined by 01.,2= (SJ)/(S2)0 and '1r= A2M1I2[4,rJ/2NA «S2)/M) 3/2]-1 were calculated for all combination~?f molecular weight M, solvent species, and temperature, where (52)0 is the value of (S2) under () conditions and NA is Avogadro's number. These two quantities should be functions of a single parameter z, usually known as the interaction parameter, which is proportional to M1I2. With the data for these quantities from the present experiments on PCP as well as from Berry's experiments on polystyrene, comparative tests of typical theories for the excluded-volume effects on dilute polymer solutions were attempted. The criteria used for this purpose were (a) linearity between MI/2 and z calculated from a, determined under fixed solvent conditions and (b) agreement between calculated and observed curves for '1r against a,. It was found that, though not perfectly, the modified Flory equation for a, \z) combined with t~~ modified Flory-:r::-rigbau~ Orofino equation for '1r (z) or Yamakawa's recent theones for these quantIties were best consistent with the experimental data chosen. The Fixman equation and the Ptitysn equation failed to obey criterion (a).

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The Dielectric Constant of cis- and trans-Decahydronaphthalene and Cyclohexane as a Function of Temperature and Frequency

Cited by 3 publications

References 2 publications

A GROMOS-Compatible Force Field for Small Organic Molecules in the Condensed Phase: The 2016H66 Parameter Set

A GROMOS-Compatible Force Field for Small Organic Molecules in the Condensed Phase: The 2016H66 Parameter Set

Direct measurement of electrostatic interactions between poly(methyl methacrylate) microspheres with optical laser tweezers

Excluded-Volume Effects in Dilute Polymer Solutions. I. Equilibrium Properties

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