We propose a method for determining effective pair potentials, incorporating n-body effects implicitly. The aim is to overcome the problem of non-additivity of solute-solute or solute-solvent interactions, so that accurate simulations of the liquid state can be made, without handling explicitly three-body or higher-order terms. The interaction potential between two charged or neutral species is evaluated from the wavefunction of the supermolecule, perturbed by the presence of the surrounding solvent. The solvent effect is simulated by means of the polarizable continuum model. The first application is a molecular dynamics study of the Fe2+ and Fe3+ cations in water. Using our effective potential we find the correct hydration number n(h) = 6, while a pair potential fitting in vacuo calculation yields n(h) = 8.
ABINITIO EFFECTIVE PAIR POTENTIALS FOR SIMULATIONS OF THE LIQUID-STATE, BASED ON THE POLARIZABLE CONTINUUM MODEL OF THE SOLVENT
FLORIS, FRANCA MARIA;PERSICO, MAURIZIO;TANI, ALESSANDRO;
1992-01-01
Abstract
We propose a method for determining effective pair potentials, incorporating n-body effects implicitly. The aim is to overcome the problem of non-additivity of solute-solute or solute-solvent interactions, so that accurate simulations of the liquid state can be made, without handling explicitly three-body or higher-order terms. The interaction potential between two charged or neutral species is evaluated from the wavefunction of the supermolecule, perturbed by the presence of the surrounding solvent. The solvent effect is simulated by means of the polarizable continuum model. The first application is a molecular dynamics study of the Fe2+ and Fe3+ cations in water. Using our effective potential we find the correct hydration number n(h) = 6, while a pair potential fitting in vacuo calculation yields n(h) = 8.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
