In this section, we provide sample configurations of SPC/E Water molecules [1] and report the various energy and force calculations for those configurations, where the coulombic contributions are computed using the traditional Ewald Summation Method [2]. These sample configurations and reference calculations can be used to validate the energy and force routines for an existing or new molecular simulation code. The discussion that follows places particular emphasis on the Ewald sum method for computing the Coulomb potential. The cutoff radius for realspace terms in this data set is 10Å.
All configurations described on this page are noncuboid. Two of the configurations are triclinic, i.e. none of the lattice angles α,β,γ are 90°, and two configurations are monoclinic, i.e., α=γ=90° and β \= 90°. The lattice angles are given in the header of each sample configuration as described in the metadata file; the user can use the cell side lengths and lattice angles to generate either a lattice matrix or the "tilt" factors often used molecular simulation.
Application of periodic boundary conditions (minimum image convention) for noncuboid simulation cells differs from that used for cuboid simulation cells. For description of the technique, consult the classic tutorial by W.R. Smith [3] or documentation of the LAMMPS molecular dynamics software [4].
The SPC/E Model represents water as a triatomic molecule with rigid bonds, i.e., both the length of the oxygenhydrogen bonds and the angle between those bonds are fixed. The triatomic molecule has a single LennardJones site centered on the oxygen atom and point charges centered on each atom:
Fig. 1: Schematic of the SPC/E Molecule.
Red and white balls indicate oxygen and hydrogen atoms, respectively. The charges, indicated in the figure, are +q for both hydrogen atoms and 2q for the oxygen atom. The dashed line is a circle of diameter σ centered on the oxygen atom, signifying the effective size of the molecule. The hydrogenoxygen bondlength is 1 Å and the hydrogenoxygenhydrogen bondangle is 109.47°. The remaining model parameters are [1]:
$$q = 0.42380~e $$
$$\sigma = 0.316555789~\textrm{nm}$$
$$\epsilon / k_B=78.19743111~K$$
The potential energy for the SPC/E model of water is:
$$ \Large E_{total}\left( \mathbf{r}^N \right) = E_{disp}\left( \mathbf{r}^N \right) + E_{LRC} + E_{coulomb}\left( \mathbf{r}^N \right) $$
The terms on the right hand side of the equality are the pair dispersion energy, the longrange correction to the pair dispersion energy, and the Coulombic potential energy, respectively. In the SPC/E Model, the pair dispersion energy is a LennardJones intermolecular potential energy, which is discussed elsewhere in the NIST Standard Reference Simulation Website. The Coulombic energy is computed using the Ewald Summation Method, which is discussed below.
The Coulombic energy, and longrange energies, may be computed using the Ewald Summation Technique, which replaces the true Coulomb potential with the following [2,5]:
$$\Large \begin{eqnarray} E_{coulomb}\left(\mathbf{r}^N\right) & = & \dfrac{1}{2} {\sum\limits_{\mathbf{n}}}^{\dagger} \sum\limits_{j=1}^N \sum\limits_{l=1}^N
\dfrac{q_j q_l}{ 4 \pi \epsilon_0} \dfrac{\text{erfc}\left(\alpha \cdot \left \mathbf{r}_{jl} + \mathbf{n}\right \right)}{\left \mathbf{r}_{jl} + \mathbf{n}\right}\\
&& +\dfrac{1}{2 \pi V} \sum\limits_{\mathbf{k} \neq \mathbf{0}} \dfrac{1}{k^2} \exp \left[\left( \dfrac{\pi k}{\alpha} \right)^2 \right] \dfrac{1}{4 \pi \epsilon_0} \cdot \left\sum\limits_{j=1}^N q_j \exp \left(2\pi i \mathbf{k} \cdot \mathbf{r}_j \right) \right^2 \\
&&  \dfrac{\alpha}{\sqrt{\pi}} \sum\limits_{j=1}^N \dfrac{q_j^2}{4 \pi \epsilon_0} \\
&& \dfrac{1}{2} {\sum\limits_{j=1}^M}^{\dagger^{1}} \sum\limits_{\kappa=1}^{N_j} \sum\limits_{\lambda=1}^{N_j} \dfrac{q_{j_\kappa} q_{j_\lambda}}{ 4 \pi \epsilon_0} \dfrac{\text{erf}\left(\alpha \cdot \left \mathbf{r}_{j_\kappa j_\lambda} \right \right)}{\left \mathbf{r}_{j_\kappa j_\lambda} \right}
\end{eqnarray}$$
The terms on the right hand side of the equality are 1) the realspace term E_{real}, 2) the Fourierspace term, E_{fourier}, 3) the self correction term E_{self,} and 4) the intramolecular term E_{intra}. We note that this form of the Ewald Summation 1) requires total charge neutrality for the configuration and 2) neglects the surface dipole term (equivalent to using the "tinfoil" or conducting surface boundary condition). The meaning of symbols in this equation are:
n  Lattice vector of periodic cell images 
k  Fourierspace vector of periodic cell images 
k  modulus of k ; k^{2} = k^{2} 
q_{j}  Value of charge at site j 
α  Ewald damping parameter 
N  Total number of charged sites 
M  Total number of molecules 
N_{j}  Total number of charged sites in molecule j 
κ, λ  Indices of sites in a single molecule 
V  Volume of the simulation cell, L_{x}L_{y}L_{z} 
ε_{0}  Permittivity of vacuum (see below) 
i  Imaginary unit, (1)^{1/2} 
r_{j}  Cartesian vector coordinate of site j 
r_{jl}  r_{j }r_{l} 
erf(x)  Error Function computed for abscissa x 
erfc(x)  Complimentary Error Function computed for abscissa x 
In this form, the superscript "†" (dagger) in E_{real} indicates that the sum skips all pairs i=j inside the original simulation cell (n = 0). The superscript "†^{1}" in E_{intra} indicates that the sum is over site pairs within molecules in the original simulation cell. Additionally, the Fourier wave vectors (k) in this equation are composed of integer multiples of the basis vectors, e.g. k = 2u+v+4w where u, v, and w are the Ewald basis vectors [6]. The Fourier space term can alternatively be written using k vectors with elements proportional to 2π. In practice, the above equation is not how the Ewald Summation is actually implemented. Typically, one makes the following assumptions/reductions to simplify the summation:
Thus, the practical implementation of the Ewald Summation is [5]:
$$\Large \begin{eqnarray} E_{coulomb}\left(\mathbf{r}^N\right) & = &
\sum\limits_{j} \sum\limits_{l>j}
\dfrac{q_j q_l}{ 4 \pi \epsilon_0} \dfrac{\text{erfc}\left(\alpha \cdot \left \mathbf{r}_{jl} \right \right)}{\left \mathbf{r}_{jl} \right} \Theta\left( r_{cut}  \left\mathbf{r}_{jl}\right \right) \\
&& +\dfrac{1}{2 \pi V} \sum\limits_{\mathbf{k} \neq \mathbf{0}} \dfrac{1}{k^2} \exp \left[\left( \dfrac{\pi k}{\alpha} \right)^2 \right] \dfrac{1}{4 \pi \epsilon_0} \cdot \left\sum\limits_{j=1}^N q_j \exp \left(2\pi i \mathbf{k} \cdot \mathbf{r}_j \right) \right^2 \\
&&  \dfrac{\alpha}{\sqrt{\pi}} \sum\limits_j \dfrac{q_j^2}{4 \pi \epsilon_0} \\
&&  \sum\limits_{j=1}^M \sum\limits_{\kappa} \sum\limits_{\lambda>\kappa} \dfrac{q_{j_\kappa} q_{j_\lambda}}{ 4 \pi \epsilon_0} \dfrac{\text{erf}\left(\alpha \cdot \left \mathbf{r}_{j_\kappa j_\lambda} \right \right)}{\left \mathbf{r}_{j_\kappa j_\lambda} \right}
\end{eqnarray}$$
We note that the realspace term now includes multiplication by the Heaviside Step Function, Θ(r_{cut}  r_{ij}), which functionally truncates that term at r_{ij} = r_{cut}.
The wave vectors in the Ewald sum are built from the Ewald basis vectors, which depend on the vectors that define the simulation cell. Calculation of the basis vectors and, ultimately, the wave vectors is described in the manual for DL_POLY Classic in section 2.4.5, "Ewald Sum." [6]
For the reference calculations given below, we use the following parameters and apply certain conditions to the calculation of both the dispersion interactions and the Ewald Summation:
α  0.2850/Å 
k_{max}  7 ; also only include k for which k^{2} < ksqmax. [See note below] 
r_{cut}  10 Å 
Truncation  
Dispersion  Truncate at r_{cut}, apply analytic longrange corrections 
Coulomb  Truncate realspace term at r_{cut} 
Boundary Conditions  Periodic and tinfoil (conducting) boundary conditions for all Cartesian Directions 
erfc(x)  Implementation of Numerical Recipes ERFCC function; Ref. 7, page 164. 
The reference calculations given below were done using fundamental constants of physics and chemistry recommended by CODATA in 2018 [8,9]. We report these constants because the calculation of each contribution to the intermolecular energy will depend, ever so slightly, on the choice of fundamental physical constants and, in particular, the number of digits in those constants that are carried in the simulation. We use the full constants (untruncated) given in the CODATA 2018 recommendation:
Name  Symbol  Value  Units 
Boltzmann Constant  k_{B}  1.380649E23  J/K 
Avogadro Constant  Na  6.02214076E+23  mol^{1} 
Planck constant  h  6.62607015E34  J s 
Elementary charge  e  1.602176634E19  C 
Permittivity of Vacuum  ε_{0}  8.8541878128E12  C^{2}/(J m) 
The Fourierspace term in the Ewald sum in sensitive to the number of wave vectors that are used. Most simulation packages reduce the number of wave vectors by discarding vectors whose squarelength exceeds some predetermined limit. For the calculations described in this page, the wave vectors included in the Ewald sum satisfy
$$k^2 < MAX\left[ \left( \dfrac{k_{x,max}}{lx} \right)^2, \left( \dfrac{k_{y,max}}{ly} \right)^2, \left( \dfrac{k_{z,max}}{lz} \right)^2 \right] $$
where lx, ly, and lz are the side lengths of the cell and kj,max is the maximum wave vector factor for the j direction. (In this example, k_{j,max }= 7 for all Cartesian directions.) To aid reproducibility, the number of wave vectors used for each sample configuration is given in the table of Section 7.
Four sample configurations of SPC/E molecules are available for download as a gzipped tarball archive. This archive contains five files: the four sample configuration files and one metadata file that explains the format of the sample configurations. These configurations should be converted to the configuration file format native to a user's simulation software.
Configuration >  1  2  3  4 
M (number of SPC/E molecules)  400  300  200  100 
Cell Type  Triclinic  Monoclinic  Triclinic  Monoclinic 
Cell Side Lengths [a, b, c] (Å)  [30 Å, 30 Å, 30 Å]  [27 Å, 30 Å, 36 Å]  [30 Å, 30 Å, 30 Å]  [36 Å, 36 Å, 36 Å] 
Cell Angles [α, β, γ] (degrees)  [100°, 95°, 75°]  [90°, 75°, 90°]  [85°, 75°, 80°]  [90°, 60°, 90°] 
Number of Wave Vectors  831  1068  838  1028 
E_{disp}/k_{B} (K)  1.11992E+05  4.32860E+04  1.44033E+04  2.50251E+04 
ELRC/k_{B} (K)  4.10919E+03  2.10561E+03
 1.02730E+03
 1.63091E+02

E_{real}/k_{B} (K)  7.27219E+05  4.76902E+05  2.97129E+05  1.71462E+05 
E_{fourier}/k_{B} (K)  4.46770E+04  4.44094E+04  2.88974E+04  2.23372E+04 
E_{self}/k_{B} (K)  1.15820E+07  8.68647E+06  5.79098E+06  2.89549E+06 
E_{intra}/k_{B} (K)  1.14354E+07  8.57652E+06  5.71768E+06  2.85884E+06 
E_{total}/k_{B} (K)  7.21254E+05  5.01259E+05  3.28153E+05  1.60912E+05 
Lastly, we note that we have reported six significant figures in each contribution to the intermolecular energy, while the software used for these calculations (a code written in FORTRAN) carried as many digits as possible within the specified machine precision. Thus, the reported E_{total} may differ in the final digits from a user's calculation.
References