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Polarizable intermolecular potentials for water and benzene interacting with halide and metal ions.

ABSTRACT: A complete derivation of polarizable intermolecular potentials based on high-level, gas-phase quantum-mechanical calculations is proposed. The importance of appreciable accuracy together with inherent simplicity represents a significant endeavor when enhancement of existing force fields for biological systems is sought. Toward this end, symmetry-adapted perturbation theory (SAPT) can provide an expansion of the total interaction energy into physically meaningful e.g. electrostatic, induction and van der Waals terms. Each contribution can be readily compared with its counterpart in classical force fields. Since the complexity of the different intermolecular terms cannot be fully embraced using a minimalist description, it is necessary to resort to polyvalent expressions capable of encapsulating overlooked contributions from the quantum-mechanical expansion. This choice results in consistent force field components that reflect the underlying physical principles of the phenomena. This simplified potential energy function is detailed and definitive guidelines are drawn. As a proof of concept, the methodology is illustrated through a series of test cases that include the interaction of water and benzene with halide and metal ions. In each case considered, the total energy is reproduced accurately over a range of biologically relevant distances.

SUBMITTER: Archambault F

PROVIDER: S-EPMC2990227 | biostudies-literature | 2009 Jan

REPOSITORIES: biostudies-literature

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Polarizable intermolecular potentials for water and benzene interacting with halide and metal ions.

Archambault Fabien F Chipot Christophe C Soteras Ignacio I Luque F Javier FJ Schulten Klaus K Dehez François F

Journal of chemical theory and computation 20090101 11

A complete derivation of polarizable intermolecular potentials based on high-level, gas-phase quantum-mechanical calculations is proposed. The importance of appreciable accuracy together with inherent simplicity represents a significant endeavor when enhancement of existing force fields for biological systems is sought. Toward this end, symmetry-adapted perturbation theory (SAPT) can provide an expansion of the total interaction energy into physically meaningful e.g. electrostatic, induction and ...[more]

PMID: 21113276

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Project description:We computed the chemical potential for some alkali metal ions (K+, Rb+, and Cs+) and two halide ions (Br- and I-) in aqueous solution at ambient T and various pressures in the range 1-8000 atm. Results were obtained from classic Monte Carlo simulations in the NPT ensemble by means of the free energy perturbation method. Here, the chemical potential is computed as the sum of a term relative to a Lennard-Jones solute and a term relative to the process in which this solute is transformed into the ion. Hydrophobic and hydrophilic features of these two components of the chemical potential show opposite behaviors under isothermal compression. The increase in pressure determines an increase in the hydrophobic component, which becomes more positive with a stronger effect for larger ions. Correspondingly, the values of the hydrophilic component become more negative for alkali ions, whereas they are only slightly affected by compression for halide ions. Hydrophobic-hydrophilic quasi-compensation in the slopes is observed for Rb+. For a smaller ion, such as K+, the dependence on pressure of the hydrophilic component is slightly dominant. For a larger ion, as observed in the cases of Cs+, Br-, and I-, the hydrophobic component assumes the determinant role. Pressure dependence of the chemical potential is little affected by corrections introduced for molecular potential truncation. This view can change for possible boundary artifacts that could have affected the static electrostatic potential. Some inference is obtained from comparison with experimental data at 1 atm on the free energy of hydration. Discrepancies show the characteristic asymmetry between cations and anions. The further addition of a correction based on the static potential significantly reduces these discrepancies with important error cancellation on the sum of chemical potentials of ions of opposite charge. The correction is applied also at higher pressures, and results are compared with those obtained by adding an alternative correction that is based on the water number density. Regardless of the ion, changes of the chemical potential induced by an increase in pressure appear to be dominated by the hydrophobic component, in particular when using the alternative correction. For bromide and iodide electrolytes, the two corrections give chemical potentials in good agreement.

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Polarizable intermolecular potentials for water and benzene interacting with halide and metal ions.

Publications

Polarizable intermolecular potentials for water and benzene interacting with halide and metal ions.

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