E3438 Journal of The Electrochemical Society, 164 (11) E3438-E3447 (2017)

JES FOCUS ISSUE ON MATHEMATICAL MODELING OF ELECTROCHEMICAL SYSTEMS AT MULTIPLE SCALES IN HONOR OF JOHN NEWMAN
Improving Continuum Models to Define Practical Limits for
Molecular Models of Electrified Interfaces
Artem Baskinz and David Prendergast∗
The Joint Center for Energy Storage Research, The Molecular Foundry, Lawrence Berkeley National Laboratory,
Berkeley, California 94720, USA

We develop a continuum theory of electrolyte solutions in contact with a metal electrode, based on a generalized free energy
functional, and use it to explore the structure of the electric double layer at different electrochemical conditions. The model captures
the effects of specific adsorption of ions and solvent polarization, and can be applied on the same footing to cases with non-zero
faradaic current, beyond the classical double-layer regime. These advances permit the prediction of peculiar character in the ion
profiles at electrode potentials near the redox level, exploration of the electrochemical stability of the interface, and differentiation
between the mechanisms of electron and ion transport and associated time scales. The developed methodology enables us to self-
consistently determine the fundamental limits for a microscopic description of biased interfaces, in terms characteristic sizes and
time scales of relevant processes, within atomistic and ab initio molecular dynamics simulations.
© The Author(s) 2017. Published by ECS. This is an open access article distributed under the terms of the Creative Commons
Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any
medium, provided the original work is properly cited. [DOI: 10.1149/2.0461711jes] All rights reserved.

Manuscript submitted April 4, 2017; revised manuscript received June 6, 2017. Published June 20, 2017. This paper is part of the
JES Focus Issue on Mathematical Modeling of Electrochemical Systems at Multiple Scales in Honor of John Newman.

As the efficiency of electrochemical conversion is dictated by the
energetics of elementary charge transfer reactions occurring at the
electrode/electrolyte interface, the formulation of methods of control
over these reactions has become the pivotal goal of fundamental ma-
terial science for advanced energy storage systems. The ultimate goal
of theoretical electrochemistry then is to explore the energetics of the
relevant processes from an atomistic perspective by means of ab initio
molecular dynamics (AIMD) where ionic and electronic components
of the system are described explicitly and are constrained by various
realistic conditions, such as the external bias, the temperature and the
electrolyte concentration. However, despite more than a decade of
efforts this goal is still far from being fulfilled.
There are several interconnected fundamental problems to resolve
before an atomistic approach could be routinely used to describe elec-
trochemistry, if only at the level of a half-cell (i.e., a single electrode-
electrolyte interface). First, there are at least three distinct regimes
of performance of the electrochemical interface and each of these is
characterized by different sets of the time and space scales: a) the
classical electric double layer (EDL) regime when no charge trans-
fer is assumed, b) the regime of an electrode at equilibrium with the
electrolyte (open circuit conditions, (OCP)) when only an exchange
current in a form of mutually compensating fluxes of charged particles
is possible, and c) the “true” electrochemical regime with a non-zero
net faradaic current. As long as the goal of atomistic simulations is
to reach a state when one would observe the actual electrochemical
reactions driven by the bias, the computational electrode potential
scanning protocol should carry the system through a set of (quasi-
)equilibrium points at which the atomistic structure is consistent with
the targeted external conditions. The key requirement for such simula-
tions is thus thermodynamic stability of the interface that encompasses
all degrees of freedom. Currently, there is no such uniform atomistic
methodology for the electrode potentials in a range of ±1 V around the
OCP since it would have to cover the processes whose characteristic
times range from attoseconds (electron transfer (ET) time) to hun-
dreds of picoseconds (solvent dielectric relaxation) at length scales
ranging from angstroms to tens of nanometers. Instead, we currently
have methodologies that either elaborate the structure of the classical
EDL1–3 or study the charge transfer per se assuming consistency be-
tween the atomistic structure of the EDL and the external conditions.4
The crossover between the two approaches is not well defined, such
∗ Electrochemical Society Member.
z
E-mail: abaskin@lbl.gov
that, for an unknown system, the simulated electrochemical activity
may be an artifact of the methodology, which relies on an initial guess
for the structure of the EDL that might prove inconsistent with the
aforementioned external conditions or some basic assumptions.
The second problem is the experimental relevance of the compu-
tational electrode potential that is a long-standing generic issue for
theoretical electrochemistry intimately related to the boundary con-
ditions of the half-cell setup. In conventional electrochemistry,5,6 the
absolute single electrode potential, E, is defined by two contributions
- the Galvani potential drop, ϕ, across the interface, which reflects
the response of the electrolyte, and the chemical potential of elec-
trons in the electrode μe . The relation between these two is not trivial
and strongly depends on the regime at which the electrode operates.
Therefore, the computational electrode potential that is comparable to
experimental values is not known a priori, since at each potential the
interface is characterized by a (unique) thermodynamic (steady) state
which is unknown a priori and which must instead be determined
a posteriori. This, in turn, implies that in contrast to the currently
adapted potentiostat schemes7–10 the electrode potential cannot be a
free external parameter and should rather be the output of a self-
consistent procedure.
The necessity to account for the response of the electrolyte in
evaluating the electrode potential itself has a profound effect on the
atomistic modeling of biased interfaces and beyond. A distinct spatial
inhomogeneity of the EDL11 at different regimes challenges the very
idea of defining the redox potentials through overall estimates of the
free energy for bulk regions of the cell. Likewise, one needs extra mea-
sures of caution when computationally assessing the electrochemical
stability of an electrolyte. Currently, the AIMD approach suffers from
unrealistic configurations of the interfaces due to the limited number
of solvent molecules explicitly included in calculations which leads
to ambiguity in the definition of the electrode potential,12 insufficient
accounting for the dielectric response of the liquid environment,13–16
erroneous assessments of the potential of zero charge (PZC),15,17,18–22
the spatial profile of the average electrostatic potential in the EDL
and its capacitance. Moreover, in practically realizable unit cells for
AIMD even an elementary fluctuation of the ion distribution or polar
solvent molecules near the interface, caused by either thermal motion
or by the loss of inventory accompanying reduction, causes a drastic
change, on the order of ±1.0 V, in the calculated electrode potential.23
Such large fluctuations of the potential might then in turn trigger an
artificial spontaneous cascade of ion reductions that might lead to a
run-away regime. To circumvent this problem, one needs to limit stud-

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 Journal of The Electrochemical Society, 164 (11) E3438-E3447 (2017)
ies to those with a large portion of concentrated electrolyte16 where
both fluctuations in the charge profile of solvent and ions are negligible
with respect to the thermodynamic average. However, calculations at
this scale may not be currently achievable due to computational over-
heads.
Lastly, the lack of a computationally tractable unified description
of the continuous electronic and discrete solute/solvent degrees of
freedom constitutes another fundamental problem for the atomistic
description of biased interfaces. Customarily, the typical condensed-
phase AIMD setup, which ideally should be open at either end away
from the interface, for electrons at the electrode and for dissolved
ions in the electrolyte, is constrained by periodic boundary condi-
tions (PBC) in conjunction with the requirement of global charge
neutrality needed to define the potential drop across the interface. A
specified concentration is realizable within the atomistic picture only
as integer ratios of solute species to solvent molecules. However, in
the conventional picture of continuous densities of electronic states
in metals, the variation of chemical potential of electrons is realiz-
able via essentially non-integer electron population. Obviously, such
a treatment is not possible for discrete ions within a finite simula-
tion. In order to represent realistic situations, the boundary conditions
(applied bias) and the molecular content of the AIMD setup must be
mutually compatible in terms of system size as well as sampling time.
For a given upper bound on system size, only a discrete and limited
set of boundary conditions is then possible and vice versa. Therefore,
in practice, the AIMD setup for a biased interface must be subjected
to additional serious limitations suiting the goals of simulations. For
instance, the steady state regime at (or beyond) the redox potential
may become inaccessible to AIMD as it would require simulations at
constant chemical potential of ions24 to replenish the lost ones, while
the actual goal usually is to study the nascent “just forming” states
resulting from irreversible ET.
As a conceptual alternative to the AIMD schemes, continuum ap-
proaches represent the electrolyte as a structureless medium and its
response to the external polarization reflects a thermodynamically av-
eraged estimate of the ion distribution with respect to distance from
the interface that is consistent with externally imposed boundary con-
ditions (e.g. the electrolyte concentration and the potential difference)
at the expense of the loss of information about local molecular-scale
spatial and dynamic variations. A class of such hybrid continuum
models that combine the continuum description of an electrolyte and
the atomistic DFT-based treatment of the electrode is based on the
generalized Poisson equation (GPE)25
 
∇ · ε (r ) ∇ −  ϕ (r ) = 0 [1]
with a smooth spatially dependent dielectric function ε(r ) 23,26–28 and
various polarizable continuum models.29–31 These mean-field models
are generalized in the framework of classical DFT32–35 in terms of
free energy functionals [ϕ; ρ+ , ρ− ] whose variation with different
boundary conditions for the electrostatic potential provides the ther-
modynamically optimal spatial characteristics of the interface. The
accounting for steric effects,36–41 short-range coulomb correlations,
and many-body interactions introduced by the self-energy corrections
to the mean-field approximation42–45 enables going beyond the stan-
dard Poisson-Boltzmann approximation (PBA)46 and explains over-
screening and crowding phenomena as well as the “camel-bell” tran-
sition in differential capacitance for ionic liquids.47,48 Depending on
a particular implementation, the corresponding ad hoc modifications
are introduced either directly into an action-like free energy functional
resulting in the Helmholtz-like form of GPE49,50 or lead to specific
changes in the boundary conditions for ϕ(r ).8,51,52
Despite these advances, these continuum models do not include the
effects of specific adsorption, thus predicting unrealistic electrostatic
potential profiles known to be dominated by specifically adsorbed
ions. More importantly, by virtue of the general theorems of elec-
trostatics, the boundary conditions of the GPE for the electrostatic
potential at the electrode, ϕ0 , and the electrode surface charge density,
σ, are uniquely connected, which makes it impossible to account for
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E3439
the effects of ET on the structure of the EDL. The same holds true
for any aspect of dynamics at the interface. This limits the scope of
continuum models to the classical EDL regime. However, the theory
does not provide estimates of its limits in terms of the applied external
bias, which may lead to an erroneous picture if the applied potential
for unknown system extends beyond the safe potential (or surface
charge) range of the EDL, when only reorganization of the electrolyte
is assumed. Another problem of continuum models is the incomplete
connection to the equilibrium thermodynamics of the metal-liquid in-
terface, whose description is usually done in terms of the unique (for
given conditions) redox potential as a starting point. In contrast, for
continuum models, the starting point is the state of zero charge of the
surface (zero potential with respect to its value in the bulk) character-
ized by flat ion density profiles which, from a thermodynamic stand
point, is a non-equilibrium state defined by the so-called potential of
zero charge (PZC). The proper evaluation of the offset between these
starting points for the electrode potential requires the introduction of
the equilibration mechanism, whether it is due to dipolar screening that
induces the accumulation of extra surface charge in the pure solvent
or the actual equilibration of the metal electrode with the electrolyte
containing its own ions. In the framework of the hybrid continuum
models that treat metal electrodes exposed to dielectric media quan-
tum mechanically47 this problem is solved only heuristically and the
ambiguity of mapping the electrode potentials of continuum models
onto the thermodynamic scale remains.
To go beyond the classical EDL regime, a combination of ET
Tafel-like kinetic equations9,53 with ion transport kinetics of contin-
uous media54 is used. Despite some progress in thermodynamically
consistent continuum transport theory,55,56 this approach lacks self-
consistency and does not resolve the effect of ET on the structure of
the double layer due to the application of a linearized version of Ohm’s
law to the steady-state regime for the homogeneous system. At this
point, the input from AIMD that provides immediate access to con-
figurational and even chemical/electronic degrees of freedom would
be very valuable, but within current limits on length and time scales,
such atomistic scale ET events may cause changes which would push
the system far from thermodynamic equilibrium (e.g., significantly
altering concentration) thus devaluating further estimates of its char-
acteristics from AIMD.
Due to the obvious complementary character of the AIMD ap-
proach and continuum models, a self-consistent combination of these
two would permit a more realistic description of the electrode-
electrolyte interface. In particular, instead of relying on the spon-
taneous equilibration of the slow molecular subsystem, from an atom-
istic computational stand point it would be much more efficient to
have it pre-equilibrated by means of a continuum model for each
value of the external electrode potential. Likewise, by extending the
applicability of a continuum model to the regime when the electrode
potential is close to (or beyond) the redox potential would allow the
formulation of a robust computational protocol for AIMD simulations
that would avoid the pitfalls of having the molecular system far from
(quasi-)equilibrium. At the same time, using continuum models with
correct boundary conditions for ϕ(r ), one can evaluate useful criteria
relevant to AIMD, such as the minimum required size of the system
and the realistic range of the electrode potential for a given electrolyte
concentration.
In pursuit of developing such a self-consistent methodology for
modeling biased interfaces, in this work we propose a continuum
phenomenological model to describe the effects of ET on the structure
of the EDL as well as the effects of specific adsorption of ions. With
properly tuned input parameters, this advanced model should permit
both design and validation of thermodynamically consistent AIMD
simulations and enable exploration of the limits of a microscopic
description of biased interfaces.
Theory
We start with the PBA of the free energy functional
2
[ρ+ (r ), ρ− (r )], where only the coulomb potential φ = 4πε0 eε|r −r  |
 E3440 Journal of The Electrochemical Society, 164 (11) E3438-E3447 (2017)

between monovalent ions is incorporated in the energy term and
core-core repulsions are neglected. With a self-consistent mean-field
electrostatic potential ϕ(r ), the entropy term associated with solvent
molecules,39,57 and a mass conservation term defined by the chem-
ical potentials of positive and negative ions μ± ,36,37 the functional
[ϕ(r ); ρ+ , ρ− ], that from now on we will call the Gouy-Chapman
with the exclusion volume (GCEV) model, gives rise to a modi-
fied Poisson-Boltzmann equation (MPBE) with Neumann or Dirichlet
boundary conditions: ∂ϕ |
∂z z→∞
= 0, ∂ϕ |
∂z z→0
= − εσ0 ε or ϕ(0) =ϕ0 .
Here we propose to generalize this GCEV model by adding terms
describing non-electrostatic specific interactions 1 (r ) and 2 (r )
of monovalent (z = 1) ions of effective size a with the electrode
surface:
 
  ε0 ε (r )
 ϕ (r ) ; ρ± (r ) = dr − |∇ϕ|2 + eϕ (ρ+ − ρ− )
2 eϕ−1
 en b
+ 1 (r ) ρ− + 2 (r ) ρ+ − μ− ρ− − μ+ ρ+

kB T
+ dr {a 3 ρ− lna 3 ρ− + a 3 ρ+ lna 3 ρ+
a3
+ (1 − a 3 ρ− − a 3 ρ+ )ln(1 − a 3 ρ− − a 3 ρ+ )}.
[2]
By definition, 1 (r ) and 2 (r ) adsorption potentials, as a part of
the free energy functional, correspond to the interactions of ions with
the neutral electrode in the infinitely diluted limit. Therefore, these
potentials do not include any dependencies on surface coverage or
bias in contrast to the adsorption energies used in the phenomenolog-
ical electrochemistry (e.g. Frumkin isotherm58,59 ). Indirectly, 1 (r )
and 2 (r ) should depend on the bias as it tunes the overlap of the
ion frontier orbitals with the electrode surface states. However, since
we disregard the electronic structure of the electrode, these quantum
effects will be ignored here. However, the proposed model keeps the
dependencies of the free energy of adsorption of ions on the bias and
surface coverage since it operates with the self-consistent electrostatic
potential that takes into account finite size effects and all interactions
between ions except non-Coulombic ones. We also ignore repulsion
between solvent molecules and thus ignore the layering in the double
layer.60
Here, in contrast to other studies where the dielectric function is
explicitly dependent on either the electric field ε(E)61 or the elec-
tronic density of solutes26 or metal electrodes ε(ρ)49,50 causing di-
electric saturation in regions of high electric field or electronic den-
sity, we use a spatially dependent dielectric function ε(r). As has been
demonstrated,62 a smooth “step-like” function ε(z) which decays from
its bulk value to the high frequency limit in the vicinity of the elec-
trode (at sufficiently high surface electron density σ) can accurately
reproduce a response consistent with Booth’s ansatz for ε(E). In this
way, we ignore the dependence of ε(z) on the surface charge density,
which will, however, be reflected in an underestimation of the differ-
ential capacitance in the small regime of electrode potentials around
PZC.
The variation δ = 0 and δρδ± = 0 leads to the modified Poisson-
δϕ
Boltzmann equation (MPBE) that reads as follows:
−eϕ−2
e kB T
− e kB T
∇ · ε (r ) ∇ϕ (r ) =  eϕ− 
ε0 1 −eϕ−2
1 − 2a 3 n b + a 3 n b e k B T + e k B T
[3]
where n b is the bulk concentration of the ions and a is the characteristic
size of the solvated ion. Its solution defines the extreme saddle point
of the functional  and spatial profiles ρ± for counterions that become
dependent on each other. As both ρ+ and ρ− are usually complex func-
tions of coordinates parametrized by the electrode potential, it is more
convenient to explore the properties of the model by analyzing the
“phase relationship” f (ρ+ , ρ− ) = 0. For the Gouy-Chapman model
(as a → 0), the phase relation is well known ρ+ ρ− = n 2b .46,47 As we
found, in the GCEV model36 ρ+ and ρ− are dependent through the
relation ρ+nρ2 − = ( 1−a1−2a
3 ρ −a 3 ρ
+ − 2
3n ) . Due to the fundamental symmetry of
b b
the coulomb interactions, the common feature of this class of models
is that f (ρ+ , ρ− ) = 0 is independent on the boundary conditions, as it
is exemplified in Fig. 1a. The inversion symmetry ρ+ ↔ ρ− is guaran-
teed by the equal size of the ions. The introduction of non-electrostatic
interactions 1 (r ) and 2 (r ) results in the concomitant modifications
of f (ρ+ , ρ− ) = 0 which now reflects the interplay between adsorption
potentials, electrostatic forces and the effects of volume exclusion. As
a consequence, the phase relation becomes dependent on the electrode
potential ϕ0 (see Fig. 1b).
Eq. 2 describes the double layer operating as an ideal non-
linear capacitor. As the electrochemical potential of electrons

Figure 1. “Phase relationships” f (ρ+ , ρ− ) = 0 for ion concentrations. a) The original GCEV model. Intervals of potentials are shown by dashed arrows. Maximum
concentration ρ+ = ρ− = 13.28 M. b) Continuum model developed in this paper (see Eqs. 7–8). A symmetrical case when 1 = 2
= 0 is shown, the adsorption
energy E ads = 0.1 eV (for details of potentials see text). As the electrode potential |ϕ| increases, the phase relation resembles more and more the relation
for the GCEV model. Orange, red and pink colors are for positive electrode potentials; light blue, blue and violet are for negative potentials. For both models,
a = 5Å, n b = 2M, ε = 80. Green and red shaded areas mark regions that are electrostatically allowed and forbidden, respectively.

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 Journal of The Electrochemical Society, 164 (11) E3438-E3447 (2017) E3441

approaches the reduction level defined for the reaction O + e− → R whose variation gives a new MPBE:
as −eφr ed +  O (φr ed ) =  R (φr ed ), at a certain overpotential one
would expect non-zero faradaic current and significant changes in the ∇ · ε (r ) ∇ϕ (r )
⎛ ⎞
structure of the double layer associated with the “leakage” of the ca- eϕ−1
pacitor. However, with a single self-consistent MPBE it is impossible
to capture these effects as explained above as a general property of
equations of electrostatics.
To resolve this issue, we introduce a simplified kinetic equation
which describes the time evolution of the concentration of the re-
ducing species, ρ+ , that is characterized by two different time scales.
The kinetics of the forward reduction process ρ+ → ρ0 is character-
ized by τ→ whereas the kinetics of the backward oxidation processes
ρ0 → ρ+ is associated with τ← . Here, ρ0 is the time and spatially de-
pendent concentration of the reduced species. Finally, TD introduces
the kinetics related to the migration/diffusion of ions in the double
layer. For simplicity’s sake, here we consider only the effect of cation
reduction. The equation reads as follows:
∂ρ+ (z, t) c̃ (z) ρ+ (z, 0) − ρ+ (z, t)
=− ρ+ (z, t) +
∂t τ→ TD
c̃ (z)
+ (ρ+ (z, 0) − ρ+ (z, t)) ,
τ←
where c̃(z) describes the portion of ρ+ (z, t) or ρ0 (z, t) that gets re-
duced/oxidized at coordinate z. Here we assume a tunneling regime
− z
when c̃(z) = e a0 , and a0 specifies the “depth” of the layer where
ρ+ (z) effectively reduces/oxidizes. The function c̃(z) reflects the
mechanism of the electrochemical process. ρ+ (z, 0) is the initial cation
concentration profile corresponding to the ideal capacitor regime (as
defined by the solution of the MPBE above). Thus, the first two terms
in Eq. 4 describe the competition between the spatially dependent ET
and the thermodynamic force bringing new cations from the bulk elec-
trolyte to restore the initial profile that corresponds to the extremum
for the free energy functional of Eq. 2. The last term in Eq. 4 describes
the oxidation rate of newly reduced ρ0 (z, t). Here we also neglect the
effect of the accumulated ρ+ (z, t) and do not consider any mechanism
of diffusion from the surface. Note, that the PBA does not take into
account any aspects of dynamics. The combination of Eqs. 3 and 4
is not self-consistent, yet provides an approximate way to include the
effects of ET on the structure of the EDL.
At steady state,
c̃(z)
τ→
+ 1
ρ+ (z, ∞) ≡ ρ∗+ (z) = ρ+ (z, 0)
TD
[5] and σi is the charge density connected with the specifically adsorbed
c̃ (z) 1
τ→
+ 1
τ←
Finally, the ET times, τ→ and τ← depend on the difference between the
reduction level eφr ed and the electrochemical potentials of electron.
We assume that
eφr ed −μe (ϕ)
τ→ (ϕ) = τ0 e kB T
and τ← (ϕ) =
τ→ (ϕ)
In order to find the self-consistent solution for the electrostatic
potential as well as for the corresponding density profiles for anions,
we rewrite the free energy functional ∗ [ϕ(r ); ρ− (r )] with the fixed
cation spatial profile ρ∗+ (z)
 
en b ⎝ e kB T   ρ ∗
(z)
= 1 − a 3 ρ∗+ (z) − + ⎠
ε0 eϕ−1
1 − 2a 3 n b + a 3 n b e k B T nb
[8]
with the same boundary conditions as for Eq. 3. Eqs. 3, 5, 6 and
8 constitute the formalism which describes the effects of ET on the
structure of the double layer.
Results and Discussion
Effects of specific adsorption and electron transfer.—Eq. 3 cap-
tures several important features. The double-layer capacitance is dom-
inated by the effects of adsorption of ions.63 In Fig. 2 we show
the progression of differential capacitance, Cdi f = dϕ dσ
, for two
different adsorption energies of anions with E ads = 3k B T (blue
solid line) and E ads = 6k B T (red solid curves) for concentrations
[4] n b = 0.1, 0.2, 0.4 and 0.8 M. Here we assume that the electrode
is “the sticky surface” for anions with the adsorption energy profile
defined by 1 = E ads (1 − e−k(z−z0 ) )2 − E ads where k = 2Å−1 and
z 0 = 0, and no specific adsorption for cations 2 = 0. The effec-
tive size of ions is set as a = 3Å far enough from the saturation
limit ∼10Å at n b = 0.8 M which should guarantee the minimum
of Cdif , at the PZC in the absence of ion adsorption, dielectric con-
stant ε = 80 and temperature T = 300K . For sufficiently negative
electrode potentials ϕ < −0.15 eV, the effects of specific adsorption
vanish, and both pictures give the same results. However, at higher
adsorption energy of anions, one sees not only the shift of the min-
ima of Cdif , but also a peculiar “camel-bell” transition.37,38,40 Similar
trends were experimentally observed for aqueous solutions of simple
anions for polycrystalline Ag-electrodes.63,64 The values of Cdif are
overestimated. However, Eq. 3 with advanced adsorption and steric
repulsion potentials65,66 may easily produce, without introducing the
ad hoc term rε0 , the effect of the compact Helmholtz layer with a linear
profile of the electrostatic potential resulting in more realistic values
of Cdif .
Another useful feature of Eq. 3 is that it allows us, in princi-
ple, to estimate the Esin-Markov coefficient and the electrosorption
valency l B = −z( ∂σ M
) , where σ M is the charge density on the metal
∂σi E
+ 1
TD species,64,67 and to compare that with experimental values of l B . That
opens the way to theoretically evaluate the charge transfer coeffi-
cient, λ, and refine the model based on experimental results.68,69 With
both the effects of lattice saturation and specific adsorption accounted
for, the concentration profiles ρ− (z) and ρ+ (z) can be viewed as a
generalization of a Frumkin isotherm. The model presented above
τ20
[6] also naturally includes the interactions with the image charge in-
duced on the electrode surface but does not account for the contri-
bution from the “quantum capacitance”. That affects the estimates of
the PZC accordingly. Lastly, a smoothed step-like dielectric function
ε−1
ε(z) = 1 + 1+ex p(−α(z−z 26,49
similar to that found in approximate so-
0
 ))
lutions of the Poisson equation with the Booth’s-like ε(E),61,62 where
α = 5 and z 0 = 0.5Å in Eq. 3 renormalizes the overall capacitance
  ε0 ε (r )   making it more realistic as compared to that from the GCEV model,
 ϕ (r ) ; ρ± (r ) = dr − |∇ϕ|2 + eϕ ρ∗+ − ρ−
2 as shown in Fig. 2 by green and orange curves corresponding to the
 anion adsorption energies E ads = 3k B T and 6k B T , respectively.
+ 1 (r ) ρ− + 2 (r ) ρ∗+ − μ− ρ− − ρ∗+ The analysis of the model that combines the simple ET kinetic
Eq. 4 and the self-consistent Eq. 3 allows us to draw the following
 observations. At μe  φr ed (ideal capacitor regime), τ→  τ←
kB T
+ dr {a 3 ρ− lna 3 ρ− + a 3 ρ∗+ lna 3 ρ∗+ but at this electrode potential not enough ρ0 is created to drive the
a3 current in the anodic direction. The second term in Eq. 5 induces
+ (1 − a 3 ρ− − a 3 ρ∗+ )ln(1 − a 3 ρ− − a 3 ρ∗+ )}, asymmetry between ρ+ (z) and ρ0 (z) that leads to non-zero current at
μe (ϕ) = φr ed , where τ→ = τ← = τ0 . Further decrease of the electrode
[7] potential promotes a cathodic current by decreasing τ→ but at the same

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 E3442 Journal of The Electrochemical Society, 164 (11) E3438-E3447 (2017)

Figure 2. Progression of differential capacitances with specific adsorption of anions. a) Adsorption energies Eads = 3k B T (blue solid line), dielectric constant
ε = 80, b) E ads = 6k B T (red solid curves) dielectric constant ε = 80, c) Eads = 3k B T (solid green line), ε = ε(z), d) E ads = 6k B T , ε = ε(z) (orange solid line)
for bulk concentrations n = 0.1, 0.2, 0.4 and 0.8 M. Black dashed curves - differential capacitance of the GCEV model.36

time it depletes the cation concentration next to the electrode, slowing
down reduction. On the other hand, the reduced ρ0 will be less and less
likely oxidized due to the increase of τ← . This competition of rival
factors results in a steady state current which depends on the initial
mutual alignment of the reduction level φr ed and initial E f . However,
at the finite scanning rate of voltammetry, the current may appreciably
deviate from the steady magnitude and should exhibit hysteresis.
In Fig. 3 we show the effects of ET on the ion concentration pro-
files and the electrostatic potential as compared to the regular EDL
predicted by the GCEV model. No effects of specific adsorption are
included. Different electrochemical conditions are defined by parame-
ter 0 (see the inset of Fig. 3) which specifies the offset between Ef of
the neutral electrode and the reduction potential φr ed and thus its elec-
trochemical activity. As τ0 and T D are set as 1 and 100, respectively,
τ→ = τ← = TD at the potential corresponding to 0 = 0.115eV.
At the potentials φred − μe ≤ 0.115 eV, τ→ ≤ TD and the EDL
behavior starts deviating from that of the ideal capacitor. A peculiar
non-monotonic concentration profile of anions (Fig. 2c) is a result
of the competition between attraction to cations, repulsion from the
negatively charged electrode and steric factors which preclude high
local concentration of both types of ions at the same distance. If the
backward oxidation of ρ0 is suppressed (τ←  τ→ at μe = φred ),
the model predicts the nearly full depletion of ρ+ at z = 0 which
at small 0 may lead to the depolarization of the electrode surface
(σ > 0 at ϕ < 0). The model also predicts the regimes at which the
electrode surface is covered by anions even at ϕ < 0.
The effects of ET impact the differential capacitance of the dou-
ble layer. Though the differential capacitance is strictly speaking well
defined only in the range of potentials within the classical double
layer, here we show the “renormalization” of surface charge density
in the presence of non-zero current. In Fig. 4 we show the correspond-
ing modifications of Cdif as the electrode potential approaches φr ed .
Focusing first on the effect of varying solution concentration (blue
curves) at constant offset 0 = 0.22 and at φr ed − μe ≈ k B T (below
−0.15 V ), we notice Cdif drops dramatically (compare with Fig. 1 or
the dashed curves). Next, as the electrochemical activity, 0 , of the
electrode increases progressively (red curves), we see changes in Cdif
in the same voltage range. The inclusion of the effects of specific ad-
sorption and solvent polarization mixed with ET will have a profound
effect on the EDL structure affecting the PZC. In principle, the param-
eters for the presented model can be extracted from EIS experiments
mapping the characteristics of ET resistance and ion diffusion with
corresponding characteristic time scales TD , τ→ and τ← .
AIMD simulations of the biased interface: fundamental limits
and implications from continuum models.—Thermodynamic consis-
tency with interfacial electrochemical boundary conditions requires
that AIMD simulations meet several interconnected requirements. Let
us make some common assumptions on typical AIMD calculations
relevant to condensed phase interfacial studies of half-cells: (1) We
employ periodic boundary conditions (PBCs), where the semi-infinite
solid electrode surface is modeled as a sufficiently thick slab of atoms
extended periodically in the plane of the surface – typically less than
10 atomic layers may suffice for most simple metals. These PBCs
define two relevant characteristics of the associated orthorhombic su-
percell - its overall length in the direction of the surface normal, l, and
its area in the plane of the surface, S; (2) The liquid/electrolyte region
is defined by another “slab” sufficiently thick to preserve a particular
volume with bulk behavior (material density, molecular diffusivity, av-
erage concentration and spatial correlation of dissolved species, etc.)
at some distance from the electrode surface; (3) overall the length
of the AIMD simulation cell is sufficient to also include interfacial
phenomena different from the bulk behavior in both the electrode and
electrolyte, for example, to encompass the electric double layer. If we
assume the electrode to be metallic, then these interfacial differences
will be limited (excluding the outermost layer of metal atoms) to the
electrolyte – this would not be so for any insulating or semiconducting
layers formed on the electrode surface, perhaps as models of a solid
electrolyte interphase. So, the volume of the AIMD supercell can be
obtained as the product S (lsolid +linterface +lbulk ). Within this volume we

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 Journal of The Electrochemical Society, 164 (11) E3438-E3447 (2017) E3443

Figure 3. Structure of the double layer. Concentration profiles of cations (red curves), anions (blue curves) and electrostatic potential (black curves) at different
electrode potentials and electrochemical conditions defined by 0 (see the inset) with (solid curves) and without (dashed curves) effects of ET. The electrolyte
concentration n b = 6 M, ion size a = 5Å, The “depth” length of the ET function c̃(z) is a0 = 0.2Å, the ET time τ0 = 1, migration time TD = 100. The
ration of τ+ /TD and the surface charge density σ are shown for each electrode potential w/o the effects of ET. a) and b) ϕ = −0.1, −0.185, −0.3 V . c) and d)
ϕ = −0.01, −0.025, and −0.05 V .

require global charge neutrality, based on the three kinds of charge
carriers which meet at the interface, such that n e = N+ − N− , where
N+ and N− are the number of cations and anions in the liquid, respec-
tively, and n e is the amount of excess electronic charge (electrons if
positive, holes if negative).
In all that follows, we will refer to one specific interface as the
active electrochemical interface. Clearly, a slab of finite thickness
has two sides that meet the electrolyte under PBCs, but we assume
that at finite bias, inversion symmetry is broken and only one surface
becomes electrified. This can be achieved by the initial arrangement
of the ion distribution, which should mimic the profile determined
from the continuum model. Specifically, within the “bulk” electrolyte
volume, S lbulk , there are an equal number of cations and anion, while
the mismatch defining the number of surface electrons, ne , is limited
to the interfacial region, Slinterface . We assume that thermal fluctuations
are insufficient to drive the system out of this metastable state toward
the lower energy state with the excess charge split evenly on either
side of the slab.
By virtue of the necessarily discrete nature of the atomistic descrip-
tion of the ions, the charge neutrality requirement limits n e to integer
values and sets some minimum limits on the surface change density at
the electrode (described below). In the absence of an explicit reference
electrode, an internal reference for the half-cell AIMD setup is pro-
vided by the calculated, self-consistent, thermodynamically-averaged,
electrostatic potential in the bulk region of the explicitly included elec-
trolyte. Vital characteristics of the supercell are: its ability to screen
electric fields, such as that generated by the electronic surface charge
density, within a certain length lscr and a particular time scale. At ther-
mal equilibrium, material specifics define these length and time scales
as the Debye length, δ D , and the slowest relaxation time τx 70 (e.g. the
inverse rotational diffusion coefficient), respectively. Under an exter-
nal bias, the Gouy-Chapman length l GC 71 dictates the variation of the
distributions of ions and defines the number of ionic species within a
layer next to the electrode as compared to its value in the bulk. Thus
l GC via the link with the surface charge density limits the minimum
electrolyte concentration and the electrode surface area, S, connecting
the efficiency of the time averaging over the simulation length and the
“static” (or relaxed) picture given by continuum models. Though the
applicability of these lengths and time scales is, strictly speaking, lim-
ited by the idealized diluted electrolytes (ionic strength below 0.2 M,
electrode potentials below 80 mV72 ), they can still be used to estimate
the critical parameters of AIMD setups.
The combination of the aforementioned conditions leads to the
following limitations for the AIMD simulations of biased interfaces
(here we consider the charging of the electrode with electrons).

1. Due to the discrete nature of the ionic charge imbalance, both

Figure 4. Effects of ET on the differential capacitance. Dashed curves – no
ET, solid lines – with ET. Blue curves – progression of Cdif for ion con-
centrations n b = 0.1, 0.2, 0.4 and 0.8 M. φr ed − E f = 0.22 eV . Ion
size a = 3Å. Red curves – the effect of the electrochemical activity of the
surface. Ion size a = 5Å. The concentration n b = 6M. The offsets are
0 = 0.25, 0.24, 0.23, 0.22 eV .
the surface charge density, σ, and the electrode potential, ϕ, are
quantized values with the minimum “quanta” σ = ±1/S and
ϕ = L(σ) defined by the capacitance of the EDL. For the
AIMD setups with a fixed number of ions, the maximum im-
balance n e ≤ N−T − 1, where N−T is the total number of anions

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 E3444 Journal of The Electrochemical Society, 164 (11) E3438-E3447 (2017)
defined by the bulk electrolyte concentration, n b , and the size of
the interfacial region.
2. The surface area has to be within Smin ≤ S ≤ Smax range.
Smax is limited by the computational feasibility of the simulation
(maximum number of solvent molecules). For aqueous solution,
Smax [Å2 ] ≤ Nwater 29.89L[Å]
, where L is the length of the solution part
of the cell. The lowest limit for Smin is dictated by the minimum
electrode potential ϕmin (in electrochemical scale) that has to be
in the safe EDL region at least several k B T away from reduc-
tion potential φr ed for the minimum ionic imbalance (n e = 1).
However, for an AIMD practitioner Smin may rather be limited
by other factors such as incompatibility of the bulk electrolyte
concentration with the target bias (see below).
3. In either conditions (constant surface charge density73 or constant
chemical potential of electrons74 ), the size of the cell must be such
that thermal fluctuations of polar solvent molecules and ionic
species do not exceed a certain limit. As has been shown,73 for
a pure polar solvent, the probability distribution of the electrode
potential derived from Marcus theory for linear solvent polariza-
tion has a Gaussian shape with a standard deviation independent
of the actual electrode potential. In the realistic AIMD setup with
water (L = 10Å and S = 100Å2 , 32 water  molecules), the
standard deviation of the electrode potential ϕ2  = 0.51 V ,
which is much larger than the thermal energy. Clearly, for such a
small AIMD setup, correspondingly large fluctuations might eas-
ily induce electron transfer events across the solid-liquid interface
with little correspondence to reality. Explicit inclusion of ionic
species8,9 may introduce even more serious problems, since the
interfacial fluctuations of discrete ion distributions may induce
even larger fluctuations of the electrode potential or may shift the
energy of a LUMO orbital for a molecular species in the elec-
trolyte into resonance with the electrode Fermi level. The rigorous
estimations of the effects of fluctuations is a non-trivial prob-
lem that requires one to use not only the fluctuation-dissipation
theorem70 which relates the differential capacitance and the vari-
ance of the total charge q 2  = Cdi f k B T or the electrode po-
tential ϕ2  = Ck BdiTf but some other kinetic characteristics of the
solution, e.g. diffusion constants, viscosity, etc. To the best of
our knowledge the general expression for the spatially dependent
standard deviation of ion densities ρ2± (z; σ) is unknown for the
advanced continuum models and will be a subject of future stud-
ies. Note that the necessary constants in the ET model described
above may be determined from consistent AIMD simulations, es-
pecially the position in energy of available electronic levels in the
electrolyte and estimates of the time constants for charge transfer
based on constrained electronic structure calculations.75
4. To properly describe the interface, the cell has to comprise the
interfacial region characterized by lscr (screening length) and the
bulk region whose dimensions allow for the√proper description of
ion-ion correlations at finite concentration ( S ≥ 2lc , lbulk ≥ 2lc ,
where lc is the ion-ion correlation length and lbulk is the length
of the bulk electrolyte region, defined already). With a fixed
number of ions in the simulation cell, the bulk region will ef-
fectively work as a buffer to damp oscillation in the ion pro-
file at the interface which is in fact what may define its dimen-
sion. To withstand a certain potential drop across the interface,
there will be corresponding ion density profiles with a spatial
ionic imbalance. For a monovalent binary aqueous electrolyte
(ε = 80, T = 300 K , n b = 1M, z = 1, δ D ≈ 3Å) con-
tained in the simulation cell with a size L = 10Å and S = 150Å2 ,
the minimum surface charge density σmin = 10.7 μC/ cm 2 . How-
ever, if the concentration is n b = 1M, this unit cell contains only
one ion pair which along with the estimates of l GC = 3.4Å at
σmin = 10.7 μC/ cm 2 suggests that this AIMD setup is a very
rough representation of the physical system where the screening
of the surface charge may be obtained only at the expense of very
long simulation time. Furthermore, the strong implicit correlation
between charged species in neighboring periodic replicas of the
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supercell will generate unphysical long-ranged electrostatic er-
rors that may also prevent fair comparisons with measurements.
This example also shows that for a certain concentration the sur-
face area S may not be too small as it would require an excessive
length of the simulation cell L to accommodate the appropriate
number of ions to support the interfacial ionic imbalance which
is again tantamount to a very long simulation time.
Here, we propose to use our continuum model to assess the critical
limits for the AIMD setup to meet the requirements of thermody-
namic stability from the standpoint of the bias. Specifically, to de-
termine practicable AIMD simulations, we focus on the size of the
AIMD setup in terms of number of atoms, which, for condensed phase
systems, is directly linked to spatial dimensions via material density.
For the moment, we omit discussion of the necessary time scales for
converged thermodynamic averaging, with the expectation that this is
merely an overall multiplicative factor in determining computational
cost and tractability.
For comparison, we use both the GCEV model and our model that
includes the effects of the specific adsorption of anions and spatial
dependence of the dielectric function. Other effects, such as ET can be
included in a similar way. The input parameters (bulk concentration,
dielectric function and surface charge density) are used to obtain
the information about the self-consistent electrode potential and the
ion density distributions that are further used as an input for the
AIMD simulations. In this way, we can try to reproduce the pre-
equilibrated state compatible with the boundary conditions and skip
the slow equilibration of the molecular subsystem. The AIMD is the
then used to obtain anew the ion profiles as an updated input for
the continuum model. In Fig. 5 we show the conceptual scheme of
input/output parameters.
To assess the screening length, lscr , we require that at each induced
surface charge density, σ, the deviation of the average electrostatic
potential at that distance from the overall potential drop meets the
condition | ϕ(lϕ
scr )
| ≤ 0.02 which guarantees the approximate neutrality
of the interfacial region. To define the length of the bulk region, lb ,
we require it to be long enough and contain enough ions to support
the ionic imbalance and preserve approximately the bulk solution
concentration in the overall cell: N+T = 2N+c , N−T = N+T − n e , where
N±T – total number of ions of each sign in the cell L = lscr + lb ,
N±c = S ∫l0scr ρc± (z)dz – is the number of ions in the interfacial region
predicted by the continuum model. For a given surface area S we
evaluate the length of the cell L as a function of the concentration for
each value of the charge imbalance n e and thus evaluate the minimum
size of the cell for each value of the electrode potential. For the model
that includes the effect of specific adsorption of anions and spatial
variance of dielectric function we use the parameters described below.
1 = E ads (1 − e−k(z−z0 ) )2 − E ads (k = 2Å−1 , E ads = 0.5 eV and
ε−1 
z 0 = 0). ε(z) = 1 + 1+ex p(−α(z−z  )) , where α = 5, and z 0 = 0.5Å. The
0
effective size of ions is set as a = 4Å, dielectric constant ε = 80 and
temperature T = 300K . Empirically we found that lscr ∼ √1nb and
has a very weak dependence on the boundary conditions similarly to
what one would expect from the Debye screening.
In Fig. 6a we show the results obtained with the GCEV model
μC μC
for the surface charge density 8 cm 2 ≤ σ ≤ 40 cm 2 keeping the over-
all neutrality of the cell. The estimates show that for concentrations
n b ≤ 0.5 M AIMD simulations would require excessively long cells
that for the higher charge imbalance (e.g. n e = 5) can easily ex-
ceed computational feasibility (150Å → 1000 water molecules, black
dashed line). Alternatively, these limitations can be seen in terms of
maximum applied potential (see Fig. 5b) that cell can support. For con-
centration 0.5 M, 1 M and 2 M, ϕmax is 0.12 V, 0.2 V and 0.38 V ,
respectively. As long as the GCEV continuum model captures well
the electrolyte response, these estimates seriously challenge the at-
tempts to simulate atomistically thermodynamically stable interfaces.
To meet the stability requirements, the short AIMD cells (≤ 20Å)
can be used to simulate interfaces only at the potentials smaller or
 Journal of The Electrochemical Society, 164 (11) E3438-E3447 (2017) E3445

Figure 5. The scheme of the hybrid methodology. Input parameters and the flow of input/output for both the continuum model and the AIMD simulations are
shown. Integer numbers of ions N±c (z i ) in the interfacial layers of width a are used to restore the spatial profile of ions in the AIMD setup. The schematics of
the ion-ion pair correlation function with the characteristic correlation length lc is shown to emphasize the critical length scale of the bulk region of the AIMD
setup.

Figure 6. Estimates of critical parameters of AIMD setups based on the continuum models. (a,b) The GCEV model. (c,d) The continuum model developed in
this paper (for parameters see the text). (a,c) The minimum length of the liquid part of the cell (surface area S = 200Å2 ) as a function of bulk concentration of
monovalent electrolyte for different charge imbalance n e = 1, 2, 3, 4, 5 ē. (b,d) The minimum length of the liquid part of the cell as a function of maximum applied
potential for different bulk concentrations n b = 0.5, 1, 2, 3, 4, 5 M. Lengths are evaluated at discrete values of potentials corresponding to the charge imbalance
n e . Solid lines are drawn to guide the eye. Black dashed line shows the computational “feasibility” limit of 1000 water molecule per cell (∼ =150Å).

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 E3446 Journal of The Electrochemical Society, 164 (11) E3438-E3447 (2017)
comparable to kT = 0.025 V which may not be relevant for any
practical applications.
The consideration of more realistic continuum models helps to
alleviate these severe size limitations. In Figs. 6c, 6d we show the
estimates of the cell sizes when specific adsorption of ions and spatial
variance of dielectric function are accounted for. The strong specific
adsorption (E ads = 0.5 eV ) of anions reduces the variation of cell
lengths within the same range of the surface charge density (see Fig.
5c) since at these conditions the capacity is dominated by the ad-
sorption. Therefore, the biggest effect of it is expected to be well
seen at lower potentials as it is shown in Fig. 5d. Indeed, for con-
centration 0.5 M, 1 M and 2 M, ϕmax is 0.21 V, 0.42 V and 0.65 V ,
respectively. This result indicates that AIMD simulations of stable
interfaces at ϕ ∼ 0.5 V can be practicable at realistic concentrations
as they naturally include such effects.
The attempts to evaluate the size limits for interfaces at higher
biases encounter serious problems inherent to continuum models per
se. In the absence of ion-ion correlations, this simplified descrip-
tion predicts the over-packing of cations and the full depletion of
anions in the interfacial region. The problems become especially ev-
ident at lower concentrations at which N−c < 1 in the large region
(lscr ∼ 15 − 20Å). At this point, AIMD outputs should serve to re-
fine the continuum model in a self-consistent fashion to construct
eventually more realistic interfaces.
Conclusions
In the presented work we develop the model that combines the
classical continuum theory of the electric double layer with kinetic
equations to incorporate the effects of specific adsorption and electron
transfer within the formalism based on the free energy functional.
Specifically, we achieved the following results.
1) Introduction of non-electrostatic (e.g., specific adsorption) inter-
actions 1 and 2 of ions with the electrode permits treating the
system at the level of the differential modified Poisson-Boltzmann
equation and leads to significant modifications of the “phase re-
lationship” f(ρ+ , ρ− ) = 0 and the differential capacitance of the
double layer as compared to the GCEV model.
2) Accounting for the non-linear solvent polarization effect results
in the appreciable renormalization of differential capacitance.
These advances permit direct comparison of our model to the ex-
perimental measurements of the electrode surface coverage by specifi-
cally adsorbed ions (e.g. Hurwitz-Parson method). This in turn enables
an access to the details of ion adsorption potential.
3) We show that the description of the electric double layer at elec-
trode potentials close to the redox potentials can be efficiently
performed with a formalism based on a pair of coupled modified
Poisson-Boltzmann equations. This scheme predicts the peculiar
structure of the double layer in the presence of non-zero faradaic
current and significant changes in the differential capacitance at
potentials near the redox levels. Our model is equally suitable for
either const − ϕ or const − σ boundary conditions.
When the formalism is used with the parameters obtained from ab
initio calculations and/or relevant experiments, e.g. EIS, it allows us
to merge the continuum models self-consistently with AIMD. Using
continuum models, we perform an analysis of the thermodynamic
consistency and the limiting characteristics of an AIMD setup in terms
of the cell sizes and the applied surface electron density/electrode
potential that leads us to the following results.
4) We provide estimates of AIMD cell sizes as functions of applied
potentials that meet the requirements of thermodynamic stability
of biased interfaces and compatibility of the content of the elec-
trolyte (ion concentration, number of solvent molecules) with the
target conditions.
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5) These estimates indicate that for realistic electrolyte concentra-
tions and currently used AIMD cell sizes, the validity of ab
initio approaches is limited to very small electrode potentials
(ϕmax < 0.05 V). Simulations at the higher biases would im-
ply strongly non-equilibrium configurations of the solution and
incompatibility with the targeted external conditions.
6) Estimates of the critical parameters for AIMD simulations based
on continuum models that include the effects of specific adsorp-
tion and solvent polarization show that simulations of practical
voltages (ϕ ∼ 0.1 V) are within reach of atomistic simulations but
require special computational protocols to avoid time-consuming
pre-equilibration stages.
We believe that our findings pave the way toward a self-consistent
methodology for modelling biased interfaces with the continuum level
description as an indispensable part.
Acknowledgments
This work was supported by the Joint Center for Energy Storage
Research, an Energy Innovation Hub funded by the U.S. Department
of Energy, Office of Science, Basic Energy Sciences. Portions of this
work were supported by a User Project at The Molecular Foundry
and its compute cluster (vulcan), managed by the High-Performance
Computing Services Group, at Lawrence Berkeley National Labora-
tory (LBNL), and portions of this work used the computing resources
of the National Energy Research Scientific Computing Center, LBNL,
both of which are supported by the Office of Science of the U.S. De-
partment of Energy under contract no. DE-AC02-05CH11231. Au-
thors thank Prof. J. Newman and Dr. Ph. Ross for useful discussions.
The authors declare no competing financial interest.
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