Related papers: Accounting for electronic polarization in nonpolar…
The impact of targeted replacement of individual terms in empirical force fields is quantitatively assessed for pure water, dichloromethane (DCM), and solvated K$^+$ and Cl$^-$ ions. For the electrostatics, point charges (PCs) and machine…
Recent molecular simulation and integral equation results alkali-halide ion pair potentials-of-mean-force in water are discussed. Dielectric model calculations are implemented to check that these models produce that characteristic structure…
In order to rigorously evaluate the energy and dipole moment of a certain configuration of molecules one needs to solve the Schr\"odinger equation. Repeating this for many different configurations allows one to determine the potential…
This work constructs an advanced force field, the Completely Multipolar Model (CMM), to quantitatively reproduce each term of an energy decomposition analysis (EDA) for aqueous solvated alkali metal cations and halide anions and their ion…
Efficient large-scale computer simulations of aqueous solutions require the use of accurate but simple empirical force fields for water. However, the complexity of these systems evidences the difficulties in describing solution properties…
In this work, the uncertainties in the dielectric constants of polar liquids, computed using molecular dynamics (MD) simulations, are compared for two different calculations schemes. Expressions of the uncertainty are derived for the…
The strengths and short-comings of the point-dipole model for polar fluids of spherical molecules are illustrated by considering the physically more relevant case of extended dipoles formed by two opposite charges $\pm q$ separated by a…
Force field have for decades proven to be an indispensable tool for molecular simulations which are out of reach for ab-initio methods. Recent efforts to improve the accuracy of these simulations have focused on the inclusion of many-body…
We use a coarse-grained molecular dynamics model to study the electrophoretic behaviour of flexible polyelectrolyte chains. We first characterize the static properties of the model with respect to the chain length, the polyelectrolyte…
Different schemes for the treatment of long-ranged electrostatic interactions will be examined for water simulations using the polarizable fluctuating charge potential. Several different methods are compared, including Ewald sums, potential…
Simulating water accurately has been a challenge due to the complexity of describing polarization and intermolecular charge transfer. Quantum mechanical (QM) electronic structures provide an accurate description of polarization in response…
A theoretical study of the structural and electronic properties of the chloride ion and water molecules in the first hydration shell is presented. The calculations are performed on an ensemble of configurations obtained from molecular…
The dynamics of the electrons for a molecule in solution is coupled to the dynamics of its polarizable environment, i.e., the solvent. To theoretically investigate such electronic dynamics, we have recently developed equations of motion…
A procedure is described for the precise nonrelativistic evaluation of the dipole polarizabilities of H_2^+ and D_2^+ that avoids any approximation based on the size of the electron mass relative to the nucleus mass. The procedure is…
We analyze the molecular electric dipole moments (PDMs) and static electric dipole polarizabilities of heteronuclear alkali dimers in their ground states by employing coupled-cluster theory, both in the non-relativistic and four-component…
Water molecules are traditionally regarded as passive dielectric media in electrochemical systems. In this work, we challenge this conventional perspective using molecular dynamics simulations and theoretical analysis. We show that…
We propose a fully ab initio theory to compute the electron density response under the perturbation in the local field. This method is based on our recently developed local dielectric response theory [Phys. Rev. B 92, 241107(R), 2015],…
Tasker type III polar terminations of ionic crystals carry a net surface charge as well as a dipole moment and are fundamentally unstable. In contact with electrolytes, such polar surfaces can be stabilized by adsorption of counter ions…
Drude oscillator potentials are a popular and computationally efficient class of polarizable models that represent each polarizable atom as a positively charged Drude core harmonically bound to a negatively charged Drude shell. We show that…
The driving of vibrational motion by external electric fields is a topic of continued interest, due to the possibility of assessing new or metastable material phases with desirable properties. Here, we combine ab initio molecular dynamics…