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\begin{document} |
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\title{Is the Ewald Summation necessary? \\ |
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\title{Is the Ewald summation still necessary? \\ |
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Pairwise alternatives to the accepted standard for \\ |
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long-range electrostatics} |
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\maketitle |
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\doublespacing |
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\nobibliography{} |
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\begin{abstract} |
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We investigate pairwise electrostatic interaction methods and show |
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that there are viable and computationally efficient $(\mathscr{O}(N))$ |
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alternatives to the Ewald summation for typical modern molecular |
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simulations. These methods are extended from the damped and |
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cutoff-neutralized Coulombic sum originally proposed by Wolf |
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\textit{et al.} One of these, the damped shifted force method, shows |
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cutoff-neutralized Coulombic sum originally proposed by |
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[D. Wolf, P. Keblinski, S.~R. Phillpot, and J. Eggebrecht, {\it J. Chem. Phys.} {\bf 110}, 8255 (1999)] One of these, the damped shifted force method, shows |
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a remarkable ability to reproduce the energetic and dynamic |
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characteristics exhibited by simulations employing lattice summation |
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techniques. Comparisons were performed with this and other pairwise |
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methods against the smooth particle mesh Ewald ({\sc spme}) summation to see |
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how well they reproduce the energetics and dynamics of a variety of |
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simulation types. |
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methods against the smooth particle mesh Ewald ({\sc spme}) summation |
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to see how well they reproduce the energetics and dynamics of a |
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variety of simulation types. |
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\end{abstract} |
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\newpage |
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regarding possible artifacts caused by the inherent periodicity of the |
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explicit Ewald summation.\cite{Tobias01} |
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In this paper, we focus on a new set of shifted methods devised by |
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In this paper, we focus on a new set of pairwise methods devised by |
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Wolf {\it et al.},\cite{Wolf99} which we further extend. These |
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methods along with a few other mixed methods (i.e. reaction field) are |
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compared with the smooth particle mesh Ewald |
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their usability in molecular simulations. |
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\subsection{The Ewald Sum} |
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The complete accumulation electrostatic interactions in a system with |
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The complete accumulation of the electrostatic interactions in a system with |
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periodic boundary conditions (PBC) requires the consideration of the |
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effect of all charges within a (cubic) simulation box as well as those |
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in the periodic replicas, |
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\begin{figure} |
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\centering |
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\includegraphics[width = \linewidth]{./ewaldProgression.pdf} |
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\caption{The change in the application of the Ewald sum with |
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increasing computational power. Initially, only small systems could |
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be studied, and the Ewald sum replicated the simulation box to |
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convergence. Now, much larger systems of charges are investigated |
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with fixed-distance cutoffs.} |
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\caption{The change in the need for the Ewald sum with |
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increasing computational power. A:~Initially, only small systems |
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could be studied, and the Ewald sum replicated the simulation box to |
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convergence. B:~Now, radial cutoff methods should be able to reach |
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convergence for the larger systems of charges that are common today.} |
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\label{fig:ewaldTime} |
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\end{figure} |
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charge contained within the cutoff radius is crucial for potential |
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stability. They devised a pairwise summation method that ensures |
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charge neutrality and gives results similar to those obtained with the |
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Ewald summation. The resulting shifted Coulomb potential |
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(Eq. \ref{eq:WolfPot}) includes image-charges subtracted out through |
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placement on the cutoff sphere and a distance-dependent damping |
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function (identical to that seen in the real-space portion of the |
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Ewald sum) to aid convergence |
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Ewald summation. The resulting shifted Coulomb potential includes |
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image-charges subtracted out through placement on the cutoff sphere |
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and a distance-dependent damping function (identical to that seen in |
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the real-space portion of the Ewald sum) to aid convergence |
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\begin{equation} |
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V_{\textrm{Wolf}}(r_{ij})= \frac{q_i q_j \textrm{erfc}(\alpha r_{ij})}{r_{ij}}-\lim_{r_{ij}\rightarrow R_\textrm{c}}\left\{\frac{q_iq_j \textrm{erfc}(\alpha r_{ij})}{r_{ij}}\right\}. |
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\label{eq:WolfPot} |
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between two different electrostatic summation methods, there is no |
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{\it a priori} reason for the profile to adhere to any specific |
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shape. Thus, gaussian fits were used to measure the width of the |
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resulting distributions. |
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% |
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%\begin{figure} |
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%\centering |
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%\includegraphics[width = \linewidth]{./gaussFit.pdf} |
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%\caption{Sample fit of the angular distribution of the force vectors |
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%accumulated using all of the studied systems. Gaussian fits were used |
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%to obtain values for the variance in force and torque vectors.} |
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%\label{fig:gaussian} |
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%\end{figure} |
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% |
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%Figure \ref{fig:gaussian} shows an example distribution with applied |
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%non-linear fits. The solid line is a Gaussian profile, while the |
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%dotted line is a Voigt profile, a convolution of a Gaussian and a |
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%Lorentzian. |
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%Since this distribution is a measure of angular error between two |
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%different electrostatic summation methods, there is no {\it a priori} |
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%reason for the profile to adhere to any specific shape. |
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%Gaussian fits was used to compare all the tested methods. |
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The variance ($\sigma^2$) was extracted from each of these fits and |
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was used to compare distribution widths. Values of $\sigma^2$ near |
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zero indicate vector directions indistinguishable from those |
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calculated when using the reference method ({\sc spme}). |
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resulting distributions. The variance ($\sigma^2$) was extracted from |
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each of these fits and was used to compare distribution widths. |
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Values of $\sigma^2$ near zero indicate vector directions |
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indistinguishable from those calculated when using the reference |
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method ({\sc spme}). |
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\subsection{Short-time Dynamics} |
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The effects of the same subset of alternative electrostatic methods on |
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the {\it long-time} dynamics of charged systems were evaluated using |
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the same model system (NaCl crystals at 1000K). The power spectrum |
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the same model system (NaCl crystals at 1000~K). The power spectrum |
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($I(\omega)$) was obtained via Fourier transform of the velocity |
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autocorrelation function, \begin{equation} I(\omega) = |
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\frac{1}{2\pi}\int^{\infty}_{-\infty}C_v(t)e^{-i\omega t}dt, |
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the crystal). The solid and liquid NaCl systems consisted of 500 |
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$\textrm{Na}^{+}$ and 500 $\textrm{Cl}^{-}$ ions. Configurations for |
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these systems were selected and equilibrated in the same manner as the |
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water systems. The equilibrated temperatures were 1000~K for the NaCl |
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crystal and 7000~K for the liquid. The ionic solutions were made by |
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solvating 4 (or 40) ions in a periodic box containing 1000 SPC/E water |
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molecules. Ion and water positions were then randomly swapped, and |
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the resulting configurations were again equilibrated individually. |
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Finally, for the Argon / Water ``charge void'' systems, the identities |
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of all the SPC/E waters within 6 \AA\ of the center of the |
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equilibrated water configurations were converted to argon. |
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%(Fig. \ref{fig:argonSlice}). |
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water systems. In order to introduce measurable fluctuations in the |
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configuration energy differences, the crystalline simulations were |
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equilibrated at 1000~K, near the $T_\textrm{m}$ for NaCl. The liquid |
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NaCl configurations needed to represent a fully disordered array of |
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point charges, so the high temperature of 7000~K was selected for |
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equilibration. The ionic solutions were made by solvating 4 (or 40) |
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ions in a periodic box containing 1000 SPC/E water molecules. Ion and |
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water positions were then randomly swapped, and the resulting |
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configurations were again equilibrated individually. Finally, for the |
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Argon / Water ``charge void'' systems, the identities of all the SPC/E |
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waters within 6 \AA\ of the center of the equilibrated water |
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configurations were converted to argon. |
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These procedures guaranteed us a set of representative configurations |
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from chemically-relevant systems sampled from appropriate |
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ensembles. Force field parameters for the ions and Argon were taken |
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from the force field utilized by {\sc oopse}.\cite{Meineke05} |
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|
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%\begin{figure} |
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%\centering |
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%\includegraphics[width = \linewidth]{./slice.pdf} |
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%\caption{A slice from the center of a water box used in a charge void |
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%simulation. The darkened region represents the boundary sphere within |
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%which the water molecules were converted to argon atoms.} |
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%\label{fig:argonSlice} |
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%\end{figure} |
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\subsection{Comparison of Summation Methods}\label{sec:ESMethods} |
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We compared the following alternative summation methods with results |
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(i.e. Lennard-Jones interactions) were handled in exactly the same |
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manner across all systems and configurations. |
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The althernative methods were also evaluated with three different |
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The alternative methods were also evaluated with three different |
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cutoff radii (9, 12, and 15 \AA). As noted previously, the |
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convergence parameter ($\alpha$) plays a role in the balance of the |
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real-space and reciprocal-space portions of the Ewald calculation. |
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\centering |
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\includegraphics[width = \linewidth]{./increasedDamping.pdf} |
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\caption{Effect of damping on the two lowest-frequency phonon modes in |
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the NaCl crystal at 1000K. The undamped shifted force ({\sc sf}) |
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the NaCl crystal at 1000~K. The undamped shifted force ({\sc sf}) |
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method is off by less than 10 cm$^{-1}$, and increasing the |
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electrostatic damping to 0.25 \AA$^{-1}$ gives quantitative agreement |
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with the power spectrum obtained using the Ewald sum. Overdamping can |
