TY - JOUR
T1 - Polarizable intermolecular potentials for water and benzene interacting with halide and metal ions
AU - Archambault, Fabien
AU - Chipot, Christophe
AU - Soteras, Ignacio
AU - Luque, F. Javier
AU - Schulten, Klaus
AU - Dehez, François
PY - 2009/11
Y1 - 2009/11
N2 - 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 can provide an expansion of the total interaction energy into physically meaningful, for example, 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.
AB - 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 can provide an expansion of the total interaction energy into physically meaningful, for example, 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.
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U2 - 10.1021/ct9004189
DO - 10.1021/ct9004189
M3 - Article
AN - SCOPUS:73949127149
SN - 1549-9618
VL - 5
SP - 3022
EP - 3031
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
IS - 11
ER -