Hassane El

Patrice Lahrar

Celine Simon

Merlet

published or not. The documents may come

Carbon-carbon supercapacitors: Beyond the average pore size or how electrolyte confinement and inaccessible pores affect the capacitance

Carbon-carbon supercapacitors: Beyond the average pore size or how electrolyte confinement and inaccessible pores affect the capacitance El Hassane Lahrar, 1, 2 Patrice Simon, 1, 2 and Céline Merlet 1, 2, a) 1) CIRIMAT, Université de Toulouse, CNRS, Bât. CIRIMAT, 118, route de Narbonne 31062 Toulouse cedex 9, France 2) Réseau sur le Stockage Électrochimique de l' Énergie (RS2E), Fédération de Recherche CNRS 3459, HUB de l' Énergie, Rue Baudelocque, 80039 Amiens, France Carbon-carbon supercapacitors are high power electrochemical energy storage systems which store energy through reversible ion adsorption at the electrode-electrolyte interface. Due to the complex structure of the porous carbons used as electrodes, extracting structure-property relationships in these systems remains a challenge. In this work, we conduct molecular simulations of two model supercapacitors based on nanoporous electrodes with the same average pore size, a property often used when comparing porous materials, but different morphologies. We show that the carbon with the more ordered structure, and a well defined pore size, has a much higher capacitance than the carbon with the more disordered structure, and a broader pore size distribution. We analyze the structure of the confined electrolyte and show that the ions adsorbed in the ordered carbon are present in larger quantities and are also more confined than for the disordered carbon. Both aspects favor a better charge separation and thus a larger capacitance. In addition, the disordered electrodes contain a significant amount of carbon atoms which are never in contact with the electrolyte, carry a close to zero charge and are thus not involved in the charge storage. The total quantities of adsorbed ions and degrees of confinement do not change much with the applied potential and as such, this work opens the door to computationally tractable screening strategies.

a) Electronic mail: merlet@chimie.ups-tlse.fr

I. INTRODUCTION

Electrochemical double layer capacitors (EDLCs), also known as supercapacitors, are energy storage systems attracting attention for their very high power densities, their wide range of operating temperatures and the large number of cycles of charge/discharge they can sustain. [START_REF] Zhong | A review of electrolyte materials and compositions for electrochemical supercapacitors[END_REF][START_REF] Béguin | Carbons and electrolytes for advanced supercapacitors[END_REF][START_REF] Brandt | Ionic liquids in supercapacitors[END_REF][START_REF] Lewandowski | Performance of carboncarbon supercapacitors based on organic, aqueous and ionic liquid electrolytes[END_REF] In these systems, unlike for batteries, the energy is stored through reversible ion adsorption at the electrode surface, without faradaic reactions. As a consequence, supercapacitors are characterized by a relatively low energy density compared to batteries. As the energy stored in a supercapacitor is proportional to the capacitance and the square of the operating voltage, improvements will come from optimizing the electrode/electrolyte combination, by changing the electrode material or the electrolyte nature. The electrolyte impacts both the electrochemical window, i.e. the range of voltages for which the electrolyte does not decompose, and the capacitance. However, constraints, such as safety concerns and ionic conductivity, limit the number of suitable electrolytes. [START_REF] Pal | Electrolyte selection for supercapacitive devices: a critical review[END_REF][6][START_REF] Zhu | The effect of various electrolyte cations on electrochemical performance of polypyrrole/RGO based supercapacitors[END_REF] Carbon based materials, commonly used as electrodes in EDLCs as a result of their relatively cheap cost and correct electronic conductivity, can be synthesized with a wide range of morphologies which renders it possible to explore the relationships between electrode material properties and electrochemical performance. [START_REF] Zhang | Carbon-based materials as supercapacitors electrodes[END_REF][START_REF] Simon | Capacitive energy storage in nanostructured carbon-electrolyte systems[END_REF][START_REF] Gu | Review of nanostructured carbon materials for electrochemical capacitor application: Advantages and limitations of actived carbon, carbide-derived carbon, zeolite-templated carbon, carbon aerogels, carbon nanotubes, onion-like carbon and graphene[END_REF] In idealized parallel plate capacitors consisting of metalling electrodes enclosing a dielectric medium, the capacitance is proportional to the surface area of the electrodes and inversely proportional to the distance separating the two electrodes (which could be approximated by the ion-carbon distance in supercapacitors). The use of porous carbon electrodes was thus envisioned early on as such materials can have large accessible surfaces. It should be noted though that while the presence of pores systematically increases the specific surface, it does not necessarily increase the surface accessible to the electrolyte. This has been shown, for example, by Lin et al. [START_REF] Lin | Correlation of double layer capacitance with pore structure of sol-gel derived carbon xerogel[END_REF] who studied carbons with different pore sizes (micropores and mesopores) produced via a sol-gel process. They have shown that the micropores are not accessible to ions and do not contribute to capacitance. Endo et al. [START_REF] Endo | Capacitance and pore-size distribution in aqueous and nonaqueous electrolytes using various activated carbon electrodes[END_REF] arrived at the same conclusion using a variety of activated carbons. Following these results and those of similar works [START_REF] Cazorla-Amoros | CO 2 as an adsorptive to characterize carbon molecular sieves and activated carbons[END_REF][START_REF] Sing | Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity[END_REF][START_REF] Yoshida | Electric double-layer capacitors with sheet-type polarizable electrodes and application of the capacitors[END_REF] , microporous materials were neglected for a time.

In 2006, a number of studies challenged the hypothesis that ions could not enter the micropores. Frackowiak et al. [START_REF] Frackowiak | Optimisation of supercapacitors using carbons with controlled nanotexture and nitrogen content[END_REF] synthesized a series of template carbons from mesoporous silica and showed the existence of a linear correlation between the capacitance and the volume of the micropores. In these materials, it seems that the ultramicropores, with a size less than 0.7 nm, participate in the formation of the electrochemical double layer, provided that they are in the proximity of mesopores, with a size of 3 nm or more. Wang et al. [START_REF] Wang | 3D aperiodic hierarchical porous graphitic carbon material for high-rate electrochemical capacitive energy storage[END_REF] also observed the necessity for the interconnection of pores of different sizes so that the electrolyte can enter the micropores. At the same time, Chmiola et al. [START_REF] Chmiola | Effect of pore size and surface area of carbide derived carbons on specific capacitance[END_REF] tested Carbide Derived Carbons (CDC) as electrode materials for supercapacitors with sulfuric acid H 2 SO 4 as electrolyte. These porous carbons are good model materials because of their narrow and controllable pore size distribution. The authors showed that the capacitance closely reflects the increase in microporous surface area. In addition, for these carbons, the increase in the porous volume for pores smaller than 2 nm increases the specific capacitance, while the increase in the porous volume for pores larger than 2 nm has a negative effect on capacitance. This shows that micropores not only participate in the construction of the electrical double layer, but they are also beneficial. Another study by Chmiola et al. [START_REF] Chmiola | Anomalous increase in carbon capacitance at pore sizes less than 1 nanometer[END_REF] on TiC-CDC in the presence of [NEt 4 ][BF 4 ] in acetonitrile showed that the pores with a size less than 1 nm participate largely in the capacitance. In fact, CDC allowed to reach previously unmatched capacitances of 140 F g -1 . A remarkable capacitance increase was also measured for more common activated carbons, [START_REF] Raymundo-Piñero | Relationship between the nanoporous texture of activated carbons and their capacitance properties in different electrolytes[END_REF] which shows the generality of the performance of nanopores for energy storage. This result has generated a lot of research to understand the mechanisms of charge storage within nanopores, and to understand the structural and dynamic properties of confined electrolytes. [START_REF] Béguin | Carbons and electrolytes for advanced supercapacitors[END_REF][START_REF] Salanne | Efficient storage mechanisms for building better supercapacitors[END_REF][22][START_REF] Miao | Recent advances in carbon-based supercapacitors[END_REF] Following the experimental observations of a large capacitance increase for pore sizes smaller than 1 nm, [START_REF] Chmiola | Anomalous increase in carbon capacitance at pore sizes less than 1 nanometer[END_REF][START_REF] Raymundo-Piñero | Relationship between the nanoporous texture of activated carbons and their capacitance properties in different electrolytes[END_REF]24 , many theoretical studies have been carried out to reproduce and understand this phenomenon. Molecular simulations have been conducted on a number of model supercapacitors with various electrode geometries going from planar electrodes 25-30 , slit pores [START_REF] Feng | The importance of ion size and electrode curvature on electrical double layers in ionic liquids[END_REF][START_REF] Kondrat | Accelerating charging dynamics in subnanometre pores[END_REF][START_REF] Kondrat | Pressing a spring: what does it take to maximize the energy storage in nanoporous supercapacitors?[END_REF][START_REF] Lynden-Bell | Simulations of ionic liquids, solutions, and surfaces[END_REF][START_REF] Wang | Heightdriven structure and thermodynamic properties of confined ionic liquids inside carbon nanochannels from molecular dynamics study[END_REF][START_REF] Futamura | Partial breaking of the coulombic ordering of ionic liquids confined in carbon nanopores[END_REF] or carbon nanotubes [START_REF] Shim | Nanoporous carbon supercapacitors in an ionic liquid: A computer simulation study[END_REF][START_REF] Frolov | Molecular-scale insights into the mechanisms of ionic liquids interactions with carbon nanotubes[END_REF][START_REF] Yang | Molecular simulation of electric double-layer capacitors based on carbon nanotube forests[END_REF][START_REF] Singh | A computational study of the behavior of the ionic liquid [BMIM + ][PF -6 ] confined inside multi-walled carbon nanotubes[END_REF][START_REF] Vatamanu | Molecular dynamics simulations of atomically flat and nanoporous electrodes with a molten salt electrolyte[END_REF] to more complex carbons [START_REF] Mendez-Morales | Ion-ion correlations across and between electrified graphene layers[END_REF][START_REF] Soolo | Molecular dynamics simulations of emi-bf4 in nanoporous carbon actuators[END_REF][START_REF] Merlet | On the molecular origin of supercapacitance in nanoporous carbon electrodes[END_REF][START_REF] Liu | Carbons with regular pore geometry yield fundamental insights into supercapacitor charge storage[END_REF][START_REF] Merlet | Highly confined ions store charge more efficiently in supercapacitors[END_REF] . Slit pores provide a good model geometry to study systematically the pore size dependence of the capacitance.

Among the physical insights acquired through molecular simulations, it was shown that for model slit pores the capacitance oscillates as a function of the pore size. 46-48 Such a phenomenon is nonetheless unlikely to be observed in real porous carbons with a diversity of pore sizes. Kondrat et al. have indeed shown through an analytical theory that polydispersity tends to smoothen features and monodisperse electrodes lead to the highest stored energy density. [START_REF] Kondrat | Effect of pore size and its dispersity on the energy storage in nanoporous supercapacitors[END_REF] Very recent molecular simulations works on regular tridimensional porous geometries have also shown that the pore size, [START_REF] Liu | Carbons with regular pore geometry yield fundamental insights into supercapacitor charge storage[END_REF][START_REF] Lahrar | Ionic liquids under confinement: From systematic variations of the ion and pore sizes toward an understanding of the structure and dynamics in complex porous carbons[END_REF] while being often used as a descriptor for the porous materials, is not necessarily well correlated with the structural, dynamical and capacitive properties of the systems.

In this work we conduct molecular dynamics simulations of model supercapacitors with two nanoporous carbon electrodes intentionally chosen so that they have the same average pore size but very different pore size distributions and morphologies. One of the carbon electrodes has a regular structure with a well defined pore size while the other is very disordered. We show that these characteristics lead to large differences in the capacitive properties: the ordered carbon has a much larger capacitance than the disordered one.

We correlate these observations with the interfacial properties: i) the charge separation between anions and cations seems to be facilitated in the ordered carbons, related to higher confinements, and ii) in the disordered carbon, some carbon atoms are isolated from the liquid, and hence do not participate in the charge storage. Overall, these results confirm the importance of local morphology and suggest possible directions for screening porous carbons for optimized performance.

II. METHODS

The model supercapacitors consist in two porous carbon electrodes in contact with neat [BMIM][PF 6 ] as the electrolyte. [BMIM][PF 6 ] is described by a coarse grained model with three sites for the cation and one site for the anion. [START_REF] Roy | An improved four-site ionic liquid model[END_REF] The cation geometry is kept rigid during the simulations. The intermolecular interactions are calculated as the sum of a Lennard-Jones potential and coulombic interactions:

u ij (r ij ) = 4ε ij   σ ij r ij 12 - σ ij r ij 6   + q i q j 4πε 0 r ij (1)
where r ij is the distance between sites i and j, ε 0 is the permittivity of free space, and σ ij and ε ij are the Lennard-Jones parameters. The parameters for the ions are taken from the work of Roy and Maroncelli 51 while those for the carbon atoms are taken from the article of Cole and Klein. [START_REF] Cole | The interaction between noble gases and the basal plane surface of graphite[END_REF] Cross parameters are calculated using Lorentz-Berthelot mixing rules. The ions are considered non polarizable and carry a charge of ±0.78 e. The scaling of the ion charge from ±1.0 e to ±0.78 e is used to improve the agreement between simulations and experiments for a variety of static and dynamic properties. The use of reduced charges is a computationally cheap approach to compensate for the use of a non polarizable force field. While its is obviously less accurate than the more computationally expensive polarizable force fields, [START_REF] Schröder | Comparing reduced partial charge models with polarizable simulations of ionic liquids[END_REF] it was demonstrated to be a relevant approach for a large number of systems [START_REF] Bowron | Structure and dynamics of 1-ethyl-3-methylimidazolium acetate via molecular dynamics and neutron diffraction[END_REF][START_REF] Bhargava | Refined potential model for atomistic simulations of ionic liquid[END_REF][START_REF] Chaban | Polarizability versus mobility: Atomistic force field for ionic liquids[END_REF] . The carbon structure is kept rigid as a single entity during the simulations. In reality, the structure shows a limited flexibility [START_REF] Hantel | In situ electrochemical dilatometry of carbide-derived carbons[END_REF][START_REF] Hantel | In situ electrochemical dilatometry of onion-like carbon and carbon black[END_REF][START_REF] Hantel | Parameters determining dimensional changes of porous carbons during capacitive charging[END_REF] but this aspect is difficult to integrate in the simulations conducted here which require the use of fluctuating charges on the electrodes. In a previous study on similar systems, [START_REF] Lahrar | Ionic liquids under confinement: From systematic variations of the ion and pore sizes toward an understanding of the structure and dynamics in complex porous carbons[END_REF] we have shown that a flexibility leading to relative height changes of 1% and 2% does not affect dynamical and structural properties significantly.

In many works reporting molecular dynamics simulations of model supercapacitors, the systems are built by placing a dense liquid between two empty electrodes so that once the electrolyte has filled the porous materials, the density of the liquid in the center of the system is close to the experimental density. This method has the advantage that all the equilibration can be done in NVT simulations and no geometrical changes are needed but it can potentially lead to under-filled or over-filled pores if the amount of liquid or the distance between the electrodes are not estimated properly. It is indeed not straightforward to assess the quantity of liquid which will actually enter the pores, especially for ionic liquids where ionic interactions are very strong and can limit the accessibility to the pores. In this work, we have explored a new approach to generate the starting configurations. In initial NPT simulations, the empty porous carbon of interest is surrounded by the considered ionic liquid which spontaneously wets the carbon. The density in and out of the pores can reach a realistic equilibrium thanks to the constant pressure applied to the simulation box. The filled porous carbon along with part of the surrounding liquid is then used to build the full model supercapacitor for the main NVT simulations. Details of this new methodology are given in Supporting information. The characteristics of the resulting model supercapacitors are given in Table I.

The model supercapacitors are simulated using the MetalWalls software. [START_REF] Marin-Laflèche | Metalwalls: A classical molecular dynamics software dedicated to the simulation of electrochemical systems[END_REF] . This MD code allows for the simulation of supercapacitors and is adapted to the application of 2D periodic boundary conditions. The initial configurations were generated using the fftool software [START_REF] Pádua | fftool[END_REF] and the NPT simulations used for the porous carbon filling were realised using LAMMPS. [START_REF] Plimpton | Fast parallel algorithms for short-range molecular dynamics[END_REF] The rigidity of the cation is maintained using the SHAKE algorithm. [START_REF] Ryckaert | Numerical integration of the cartesian equations of motion of a system with constraints : Molecular dynamics of n-alkanes[END_REF] After assembling the full model supercapacitor, simulations start with a constant charge equilibration step as the electrolyte. N C and N pairs are respectively the number of carbon atoms (electrodes and graphene sheets at the extremity of the box) and the number of ion pairs.

Carbon L x ( Å) L y ( Å) L z ( Å) N C N
(q = 0 for all electrode atoms) in the NVT ensemble for 2 ns. Then each system goes through a constant potential equilibration during which the electrode charge is monitored:

the end of equilibration is defined when the charge reaches a plateau. The two potential differences studied in this work are ∆ψ = 0 V and 1 V. In previously reported works, different strategies have been explored to reach equilibrium, [START_REF] Merlet | On the molecular origin of supercapacitance in nanoporous carbon electrodes[END_REF][START_REF] Liu | Carbons with regular pore geometry yield fundamental insights into supercapacitor charge storage[END_REF][START_REF] Péan | On the dynamics of charging in nanoporous carbon-based supercapacitors[END_REF][START_REF] Breitsprecher | Charge me slowly, I am in a hurry: Optimizing charge-discharge cycles in nanoporous supercapacitors[END_REF][START_REF] Fang | Simulation study of the capacitance and charging mechanisms of ionic liquid mixtures near carbon electrodes[END_REF] including the application of a constant non zero charge but, while this is fast, it is hard to handle. Here, in order to reach faster equilibrium at 1 V, we adopted a new strategy in which an initial potential of 4 V is applied for a short duration before switching to the desired potential of 1 V. Details of the methodology and its validation are given in Supporting information.

III. MODEL SUPERCAPACITORS AND THEIR INTEGRAL

CAPACITANCES

Molecular dynamics simulations of model supercapacitors consisting in two porous carbon electrodes in contact with neat [BMIM][PF 6 ] as the electrolyte were performed. The simulations conducted here have some specificities in terms of building the initial configurations and equilibrating the systems at constant potential for which details are provided in Supporting information. For each studied system, the two electrode structures are perfectly identical. For one of the supercapacitors, the electrode structure is regular and designated as "Ord" in the remainder of this article. The other supercapacitor is built with highly disordered electrodes and is designated as "Disord". Both electrode structures have the same average pore size (12.2 Å) and the same density (1 g cm -3 ). Figure 1 illustrates the model supercapacitors studied in this work.

The two porous carbons studied were taken from published works [START_REF] Deringer | Towards an atomistic understanding of disordered carbon electrode materials[END_REF][START_REF] Palmer | Modeling the structural evolution of carbide-derived carbons using quenched molecular dynamics[END_REF] and have been generated through Quench Molecular Dynamics. The Disord structure is a relatively large boundary conditions in the z direction to avoid unrealistic interactions between the positive and negative electrodes). The snapshot was generated using VMD. [START_REF] Humphrey | VMD -Visual Molecular Dynamics[END_REF] porous carbon with 3,872 atoms generated using a classical force field. Following comparisons between experimentally measured and simulated properties (e.g. coordination numbers, surface areas, average pore sizes), [START_REF] Palmer | Modeling the structural evolution of carbide-derived carbons using quenched molecular dynamics[END_REF] the Disord structure is believed to be similar to a carbide derived carbon, as used in a number of electrochemistry experiments. [START_REF] Zhong | A review of electrolyte materials and compositions for electrochemical supercapacitors[END_REF][START_REF] Béguin | Carbons and electrolytes for advanced supercapacitors[END_REF] The Ord structure is originally a much smaller porous carbon with 172 atoms generated using a machine-learning based force field developed using the Gaussian Approximated Potentials approach. [START_REF] Deringer | Machine learning based interatomic potential for amorphous carbon[END_REF] The structure is not inherently regular but rendered so by replicating the initial coordinates two times in the three dimensions leading to a much more ordered structure with 4,644 atoms. Most importantly, the pore size distribution of the Ord carbon is very narrow and unimodal while the pore size distribution for the Disord carbon is much wider as shown in Figure 2. The pore size distributions were determined with the Poreblazer software 71 using a process involving a Monte Carlo method: i) a point is placed in a random position inside the structure, ii) if the point is not colliding with any atom, a sphere containing it is gradually "inflated" until the largest sphere not overlapping with the atoms from the structure is found,

iii) these steps are repeated many times and the pore size distribution is obtained from the distribution of sphere sizes. In terms of topology, the Ord carbon is characterized by tunnels along the z axis while there are no preferred directions for the Disord carbon. The latter contains large pores but also smaller pores. The local structures of the porous materials studied are also similar, as visible from the carbon-carbon pair distribution functions which show the typical peaks of graphite like materials and rings statistics with a large proportion of 6-membered rings (see Supporting information). It is worth noting though that the peaks in the pair distributions functions of the Ord carbon are narrower than the ones of the Disord carbon, which is consistent with a more ordered structure.

After simulating the model supercapacitors at 1 V, the first property we evaluate is the integral capacitance which corresponds to the amount of charge stored on the electrodes for a given potential difference. For a single electrode, the integral capacitance is defined as:

C int = < Q tot > ∆ψ ∆ψ elec (2)
where < Q tot > is the average total charge on the electrode under a constant potential ∆ψ and ∆ψ elec is the potential drop between the electrode and the bulk electrolyte. The average electrode charge is extracted at equilibrium from the curves shown in Supporting information. While it is not straightforward to calculate precisely the potential drop between each electrode and the electrolyte, [START_REF] Péan | Single electrode capacitances of porous carbons in neat ionic liquid electrolyte at 100 • C: A combined experimental and modeling approach[END_REF] it is possible to estimate that it is half of the 1 V imposed potential. Indeed, as the system is symmetrical and the ions have similar sizes, the capacitances of the two electrodes are expected to be similar.

The total electrode charges of the Ord and Disord systems as well as the corresponding capacitances are given in Table II. To compare the two porous carbons, the capacitance values are normalized by the electrode mass as is often done for electrochemical characterization experiments. The capacitances can also be normalized by the accessible volumes or surfaces but these quantities are usually less well defined. [START_REF] Stoeckli | On the determination of surface areas in activated carbons[END_REF][START_REF] Stoeckli | Optimization of the characterization of porous carbons for supercapacitors[END_REF] According to these results, the ordered carbon has a better performance with an electrode capacitance equal to 134 F g -1 against 88 F g -1 for the disordered carbon, i.e. + 52%. The values calculated for the Disord carbon are close to the values observed experimentally, 90 F g -1 and 75 F g -1 for the negative and positive electrode respectively, for the same ionic liquid in a CDC type carbon. [START_REF] Péan | Single electrode capacitances of porous carbons in neat ionic liquid electrolyte at 100 • C: A combined experimental and modeling approach[END_REF] The values for the Ord carbon are high compared to values reported previously for ordered zeolite templated carbons [START_REF] Liu | Carbons with regular pore geometry yield fundamental insights into supercapacitor charge storage[END_REF] all in the range 60-100 F g -1 (values are doubled compared to Figure 3 in that article due to the chosen way of calculating the capacitance). The observation of a larger capacitance for the monodisperse Ord carbon is in agreement with the results of Kondrat et al. [START_REF] Kondrat | Effect of pore size and its dispersity on the energy storage in nanoporous supercapacitors[END_REF] obtained in an analytical study showing that polydispersity is expected to lead to reduced capacitances. It is worth noting that with the current simulation methodology, it is not possible to evaluate systematically the effect of pore size without changing at least partly the carbon morphology and different capacitance values could be observed for a more (or less) favorable electrode-electrolyte combination. Nevertheless, the significant deviation between the two systems simulated here provides an adequate setting to investigate the electrode-electrolyte interface and its effect on the capacitance in detail.

IV. QUANTITIES OF ADSORBED IONS AND CHARGE SEPARATION

To understand the origin of this large difference in capacitance, we explore a number of properties starting with quantities of adsorbed ions. It has been shown on several occasions that, in accordance with a simple principle of electroneutrality, the charge carried by an electrode is equal to the opposite of the charge corresponding to the adsorbed ions. 22,[START_REF] Griffin | In situ NMR and electrochemical quartz crystal microbalance techniques reveal the structure of the electrical double layer in supercapacitors[END_REF] Figure 3 gives the quantities of adsorbed ions under 0 V and 1 V applied potential differences. The values reported here are consistent with previous experimental and molecular simulations studies, 22 especially for the Disord carbon. The quantity of adsorbed ions is approximately 1.9 times larger for the Ord system compared to the Disord one for all potentials. This is consistent with our previous study showing that total numbers of adsorbed ions were larger for a range of carbons with well defined pore sizes compared to disordered carbons of a similar type to the Disord structure studied here. [START_REF] Lahrar | Ionic liquids under confinement: From systematic variations of the ion and pore sizes toward an understanding of the structure and dynamics in complex porous carbons[END_REF] The absolute ionic charge within the pores, |N cations -N anions |, is larger for the ordered structure, equal to 39.8 e (±0.8), than for the disordered structure, equal to 20.7 e (±0.8). The ionic charges are, as expected, very close to the electrode charges and within the error range. It is worth noting that the rate of change of the quantities of adsorbed ions with the applied potential, estimated from the slope of the roughly linear trends in Figure 3, is also larger for the Ord carbon (± 0.9 mmol g -1 V -1 ) compared to the Disord one (± 0.6 mmol g -1 V -1 ). All these findings combined with the faster charging dynamics observed for the Ord system (see Supporting information) seem to indicate a better pore accessibility and charge separation for this system compared to the Disord one.

The better accessibility can be due to a larger accessible volume for the Ord carbon.

Indeed, while the densities of the two carbons are similar, their pore size distributions are very different and the spatial distribution of the carbon atoms can have a large impact on the accessible volume. The geometrical accessible volumes calculated using Poreblazer 71 are 75,418 Å3 for the Ord carbon and 47,428 Å3 for the Disord carbon, i.e. 1.6 times larger for the Ord carbon. This explains partly the 1.9 times larger quantity of adsorbed ions for the Ord carbon but is not sufficient to explain it fully. Using approximate volumes of 126 Å3

for the cation and 67 Å3 for the anion (evaluated from the Lennard-Jones parameters and cation geometry), the ionic liquid is estimated to fill around 45% of the porous volume for the Ord carbon against only 31% for the Disord carbon (see Supporting information for the values at various potentials). So not only is the geometric pore volume larger for the Ord carbon, the ionic liquid is also filling it more efficiently. It is also possible that some pores in the structure are not accessible due to poor pore connectivity. It was previously shown that pore percolation can indeed play an important role in ion permeation. [START_REF] Vasilyev | Connections matter: On the importance of pore percolation for nanoporous supercapacitors[END_REF] While molecular dynamics simulations inherently take into account the effect of connectivity, as the ions can only reach pores if there is a diffusion path, it is not straightforward to assess which parts are inaccessible due to pore size or pore connectivity. It is worth noting that the percentages of pore filling estimated here are in the same range as the 40% value obtained for two neat ionic liquids ([Pyr 13 ][TFSI] and [EMI][TFSI]) in the YP-50F activated carbon [START_REF] Forse | NMR study of ion dynamics and charge storage in ionic liquid supercapacitors[END_REF] showing once again that molecular simulations are adapted to such studies. Overall, these analyses suggest that part of the porous volume and carbon atoms are not involved in charge storage in the Disord carbon.

V. DEGREES OF CONFINEMENT OF THE ELECTROLYTE IONS

The charge carried by electrode atoms and the charge separation between anions and cations depend on both the applied potential and on the electrode-electrolyte interfacial structure. To characterize the behavior of the liquid near carbon atoms we calculate the degrees of confinement (DoCs) of the ions in the pores. This property was first defined in an attempt to analyze the correlation between confinement and charge storage efficiency [START_REF] Merlet | Highly confined ions store charge more efficiently in supercapacitors[END_REF] and was later shown to be relevant in several systems to understand the capacitive properties of porous carbons. [START_REF] Liu | Carbons with regular pore geometry yield fundamental insights into supercapacitor charge storage[END_REF][START_REF] Prehal | Quantification of ion confinement and desolvation in nanoporous carbon supercapacitors with modelling and in situ X-ray scattering[END_REF] The degree of confinement is defined by the percentage of the solid angle around the ion, that is, in the first coordinating sphere, which is occupied by carbon atoms. The solid angle is normalized by the maximum value it can take so that values are always between 0% and 100%. [START_REF] Merlet | Highly confined ions store charge more efficiently in supercapacitors[END_REF] carbon. This is qualitatively in agreement with a larger capacitance for the Ord carbon since ions closer to the surface will induce a larger charge on the carbon and will also increase the screening of the ion-ion interaction by the surface which will facilitate the charge separation.

Taking the 0 V systems as a reference, it is found that, at the positive Ord electrode, the DoC of the anions remains almost the same except for the appearance of a bump towards a high degree of confinement of 19%. This peak corresponds to the formation of a population of more confined anions but the little difference between the neutral and positively charged electrodes shows that most anions are already adsorbed on the carbon surface in the neutral electrode. For the Disord structure, the change in confinement is more remarkable with a large increase in the number of anions with a DoC between 10% and 20% which is almost zero at 0 V. From 0 V to -0.5 V in the Ord electrode, the DoC distributions of the anions show a shift towards the less important degrees of confinement without modifying the shape of the curve. This suggests that the remaining anions in the electrode do not necessarily change the type of adsorption site but move away from the surface. For the Disord carbon, the shape of the curve is modified with the anions getting less confined. For cations, the variations in the distributions of DoCs with the change in potential difference are present, but less marked than for anions. That is to say that although participating in the mechanisms of adsorption/desorption and therefore in charge storage, the local structure of the confined cations is less influenced by the applied potential.

VI. ELECTRODE ATOMS CHARGES AND ACCESSIBILITY

The quantities of adsorbed ions and the degrees of confinement suggest that some parts of the disordered carbon structure are inaccessible to the ions. We now turn to a more detailed analysis of the electrode side of the interface to confirm this hypothesis and assess the consequences of such a limited accessibility on the charge storage efficiency. Figure 6 shows the probability densities of instantaneous charges on the electrode atoms for both porous carbons. It is interesting to note that the probability densities of atomic charges averaged over the entire trajectories, which are the ones considered for example by Liu et al. [START_REF] Liu | Carbons with regular pore geometry yield fundamental insights into supercapacitor charge storage[END_REF] , are very similar and are thus not reported here. These quantities once again demonstrate the large difference between both systems. For the Disord structure, many carbon atoms have a zero or close to zero charge, meaning that they do not participate efficiently in the charge storage. For the Ord structure, on the contrary, there are many charges around ± 0.01 e and only few charges near zero. Large numbers of atoms with a zero charge have also been observed in molecular simulations of zeolite templated carbons based supercapacitors [START_REF] Liu | Carbons with regular pore geometry yield fundamental insights into supercapacitor charge storage[END_REF] but the tail at large atomic charges, also seen in previous works, [START_REF] Merlet | On the molecular origin of supercapacitance in nanoporous carbon electrodes[END_REF] seems to be more specific of disordered porous carbons. The reduced number of carbon atoms with a low charge and the larger occurrence of carbon atoms with a large charge both make the charge storage more efficient in the Ord carbon. These differences could be related to local topologies which is what is investigated thereafter.

FIG. 6. Histograms of instantaneous charges on the electrode atoms for the 1 V potential difference.

Histograms of atomic charges averaged over the entire trajectory are similar to the instantaneous ones and are thus not reported here.

As the charges carried by the electrode atoms depend both on the applied potential and on the liquid nearby, it is expected that the charges with a value close to zero are located in regions of the carbon structure isolated from the liquid. In this work, a carbon atom is considered isolated if there is no ion at a distance less than R cut of its position. If there is at least one ion at a distance less than R cut , then the carbon is not considered isolated.

R cut is the distance corresponding to the limit of the first coordination shell between carbon atoms and anions or cations, i.e. the first minimum of the corresponding radial distribution function. An illustration of isolated carbon atoms is provided in Figure 7. Following this definition for isolated atoms, a carbon atom can be isolated throughout the duration of the trajectory, for a part of it or not at all. To check that isolated carbons indeed have a charge close to zero, histograms of electrode atom charges are plotted separately for carbon atoms isolated or not from the adsorbed electrolyte ions. The resulting curves are shown in Figure 8. The histograms for the carbon atoms with no ions nearby present a very sharp peak around zero confirming that isolated with the histograms of charges given in Figure 6. For the Disord carbon, it is more difficult to analyze the results. The carbon atoms surrounding the large pore present in the structure appear to be less isolated and with varying loads. On the contrary, there are zones where the carbons are isolated most of the time and these areas appear to correspond to atomic charges close to zero, in agreement with the charge histograms shown in Figure 8. It is worth noting that, as evidenced in previous works, [START_REF] Limmer | Charge fluctuations in nanoscale capacitors[END_REF] the charge on a given electrode atom does not depend only on the nearby electrolyte (and the actual ion-carbon distance) but also on the charge of neighboring electrode atoms so a direct link between the charge on a given carbon atom and the fraction of the time it is isolated is not expected to exist. Nevertheless, the analysis carried out here confirms that a porous structure with many inaccessible carbon atoms will probably show relatively poor performances in terms of capacitive properties. Since the quantity of adsorbed ions and maximal degrees of confinement do not change much with the applied potential difference, it might be possible to assess the proportion of isolated carbons already from simulations with neutral porous carbons, much less computationally expensive. If indeed correlated with the capacitance, this could serve as a screening process for assessing the electrochemical performance of a variety of carbons. This could be explored in the future using a larger set of carbons, for example those studied by Liu et al. [START_REF] Liu | Carbons with regular pore geometry yield fundamental insights into supercapacitor charge storage[END_REF] , for which capacitances have been already calculated.

VII. CONCLUSION

Molecular simulations of two model supercapacitors based on carbon electrodes with the same density and average pore size but different porous structures have been performed. The capacitance for the carbon with the more ordered structure was shown to be much larger (+ 52%) than the one for the more disordered structure. Several reasons are demonstrated to contribute to this higher capacitance for the ordered porous carbon. Firstly, the quantity of adsorbed ions initially in the pores at 0 V is higher for the Ord carbon than for the Disord carbon. Secondly, the electrolyte ions have higher degrees of confinement in the Ord carbon.

These two facts can ease the charge separation in the Ord carbon leading to a larger ionic charge. Finally, the Disord carbon contains a relatively high proportion of carbon atoms which are far from the liquid and correspond to low induced charges. While all these factors can have an impact, it is hard to assess what is their relative importance as these are not independent from each other.

The results obtained here, and in particular the potentially large impact of the initial quantity of adsorbed ions and of the proportion of electrode atoms inaccessible to the liquid, suggest potential avenues for computationally cheap methods to screen porous carbons for supercapacitor applications. If further studies confirm that the quantity of adsorbed ions and the proportion of inaccessible carbon atoms for a neutral porous carbon in contact with an electrolyte (quantities which can be assessed without resorting to computationally expensive constant potential simulations) are correlated with the capacitance in a range of suitable potentials, screening for materials leading to high stored energy densities through molecular simulations could become a tractable task. In addition, reducing the number of isolated electrode atoms might be more easily achieved using relatively ordered structures which could be obtained experimentally through templating with regular precursors. It is worth noting however that, as suggested in previous works, [START_REF] Kondrat | Effect of pore size and its dispersity on the energy storage in nanoporous supercapacitors[END_REF][START_REF] Mysyk | Saturation of subnanometer pores in an electric double-layer capacitor[END_REF] monodispersity is expected to lead to larger variations of the capacitance with the applied potential such that studies involving simulations at a range of potentials would be beneficial in the future. While the current study focuses on ionophilic pores, showing spontaneous wetting as very often observed experimentally, the case of ionophobic pores, [START_REF] Kondrat | Accelerating charging dynamics in subnanometre pores[END_REF][START_REF] Yin | Carbon electrodes with ionophobic characteristics in organic electrolyte for high-performance electric doublelayer capacitors[END_REF][START_REF] He | Observation of ion electrosorption in metal-organic framework micropores with in operando small-angle neutron scattering[END_REF] for which a different behavior can be observed, should be considered in future works. Such ionophobic structures can indeed show large stored energies at potentials while having very limited pore filling at low potentials.

FIG. 1 .

 1 FIG. 1. Model supercapacitors simulated in this work: the anions are in green, the cations in red and the carbon atoms of the electrodes in blue. Atoms colored in brown are neutral carbon atoms used to prevent ions from leaving the simulation box (in these simulations there are no periodic

FIG. 2

 2 FIG. 2. a) Pore size distributions of the two porous carbon structures used in this work. b) TheOrd carbon is characterized by a unimodal pore size distribution while c) the Disord carbon has a much wider pore size distribution. The pore size distributions were obtained using Poreblazer.[START_REF] Sarkisov | Computational structure characterisation tools in application to ordered and disordered porous materials[END_REF]

FIG. 3 .

 3 FIG. 3. Quantities of adsorbed ions in the Ord and Disord porous carbons as a function of the applied potential difference.

Figure 4

 4 illustrates ions in different environments, more or less confined.

Figure 5

 5 Figure 5 shows the distributions of DoCs of the confined ions in the two porous structures for different electrode potentials. There are two striking features in this figure. Firstly, the distributions of DoCs are much broader for the Disord carbon compared to the Ord carbon which is expected as the variety of environments is reduced in the ordered structure. Indeed, it is consistent with Figure 4 showing that, in the Ord structure, different DoCs basically correspond to larger distances to the carbon surface and not to different arrangements of the carbon atoms. Secondly, the DoCs are larger in the Ord carbon compared to the Disord

FIG. 4 .

 4 FIG. 4. Snapshots of anions (in green) in two different environments in the Ord structure. The carbon atoms are represented as solid lines along the carbon-carbon bonds with bolder lines for the carbon atoms belonging to the first coordination shell of the anions. Other anions and cations are not represented for simplicity. Small DoCs correspond to ions in the center of the pores while larger DoCs correspond to ions in the corners of the structure, i.e. in close contact with two surfaces.

FIG. 5 .

 5 FIG. 5. Distributions of DoCs for the a) anions and b) cations adsorbed in the electrodes of the Ord and Disord structures under potential differences of 0 V and 1 V. The cut-offs used to define the first coordination shell are given in Supporting information.

FIG. 7 .

 7 FIG.7. Illustration of carbon atoms isolated from the electrolyte in the Disord system. The carbon atoms are represented in grey for isolated carbon atoms, located in a region inaccessible to the anions (in green) and cations (in red), and in blue for non isolated carbon atoms.

FIG. 8 .

 8 FIG. 8. Histograms of instantaneous charges for the negative (a) and positive (b) electrodes distinguishing between carbon atoms isolated or not from the adsorbed ions.

pairs

  Ord 48.44 48.44 270.51 10,998 1,373 Disord 43.55 43.55 277.80 9,138 1,274

TABLE I .

 I Characteristics of the model supercapacitors simulated in this work with [BMIM][PF 6 ]

TABLE II

 II

	System	Electrode charge (e) Capacitance (F.g -1 )
	[BMIM][PF 6 ]/Ord	± 38.6 (± 0.5)	134
	[BMIM][PF 6 ]/Disord	± 21.2 (± 0.5)	88

. Total electrode charge and capacitance of one electrode for Ord and Disord systems under an applied potential difference of ∆ψ =1 V.

  Table III gathers the number of carbons that are isolated for the entire trajectory for the two types of carbon. For the Ord carbon, all of the

ACKNOWLEDGMENTS

This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (grant agreement no. 714581). This work was granted access to the HPC resources of CALMIP supercomputing center under the allocations P17037.

DATA AVAILABILITY

The data corresponding to the plots reported in this paper, as well as example input files for MetalWalls, are openly available in the Zenodo repository with identifier 10.5281/zenodo.5564144.

SUPPLEMENTARY MATERIAL

Pair distribution functions and ring statistics for the porous structures, additional details on the generation of initial coordinates for the model supercapacitors, a description of the equilibration strategy, estimations of porosity filling at various potentials, cut-offs for the calculations of DoCs and a visualization of the isolated electrode atoms and their charges for positive electrodes are provided in Supporting information.


Edward Ashton

Brett Gladman

J J J Kavelaars

R Lynne

Lynne Jones

K Simon

Simon Krughoff

Mike Alexandersen

Michele T Bannister

Ying-Tung Chen

Stephen Gwyn

Jean-Marc C Petit

R Lynne Jones

K Simon Krughoff

Ying- Tung Chen

Kathryn Volk

Ying-Tung Chen

OSSOS. XVII. An upper limit on the number of distant planetary objects in the Solar System

Keywords: Kuiper belt, Planetary Formation, Dwarf planets

des établissements d'enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.

Introduction

Planet formation is a complex process. Regardless of the details of how planets form, there are planets and minor bodies of all sizes observed or inferred in both the Solar System and other stellar systems. The planet building process (and subsequent collisional erosion) yields the current size distribution.

Trans-Neptunian Objects (TNOs) are icy bodies out beyond Neptune. The very upper end of the TNO size distribution is not well determined due to small number statistics; there are currently only three known Pluto-sized objects (Pluto, Eris, and captured Triton).

There were likely at least 1000 Pluto scale objects produced during planet formation in the outer Solar System [START_REF] Stern | On the number of planets in the outer solar system -Evidence of a substantial population of 1000-km bodies[END_REF][START_REF] Nesvorný | Neptune's Orbital Migration Was Grainy, Not Smooth[END_REF]. Even though almost all of these Pluto-sized minor bodies were ejected from the Solar System, it would be very surprising if the three already discovered Pluto-sized TNOs in the Solar System were all that remained. If there was another Pluto-sized or larger object in the Solar System, where eashton@phas.ubc.ca (E. Ashton) ORCID(s): 0000-0003-4143-8589 (M. Alexandersen); 0000-0003-3257-4490 (M.T. Bannister); 0000-0001-7244-6069 (Y. Chen); 0000-0001-8736-236X (K. Volk) would it be? If the object was within 165 au it had a roughly 2∕3 chance of being found by the Schwamb et al. [START_REF] Schwamb | A Search for Distant Solar System Bodies in the Region of Sedna[END_REF] (or the smaller/shallower surveys of Sheppard et al. [START_REF] Sheppard | A Southern Sky and Galactic Plane Survey for Bright Kuiper Belt Objects[END_REF], Rabinowitz et al. [START_REF] Rabinowitz | The La Silla-QUEST Kuiper Belt Survey[END_REF], Bannister [START_REF] Bannister | Bright Trans-Neptunian Objects in the Southern Sky[END_REF] and Brown et al. [START_REF] Brown | A Serendipitous All Sky Survey for Bright Objects in the Outer Solar System[END_REF]) search of the ecliptic, unless it was particularly highly inclined, or currently in front of the galactic plane. This leaves the region beyond 165 au as the most likely to yield new detections. The majority of TNO surveys are unable to detect objects moving <0.5"/hr, which corresponds to 300 au at opposition. We were thus motivated to search existing multi-night survey data looking for objects beyond these distances.

At the beginning of this 2017 investigation, the two surveys that could detect Pluto-sized or larger objects beyond 300 au distance were the Spacewatch Survey [START_REF] Larsen | The Search for Distant Objects in the Solar System Using Spacewatch[END_REF], which covered a sky area of ∼ 8,000 square degrees, and aforementioned Schwamb et al. [START_REF] Schwamb | A Search for Distant Solar System Bodies in the Region of Sedna[END_REF] survey, which covered ∼12,000 square degrees. Larsen et al. [START_REF] Larsen | The Search for Distant Objects in the Solar System Using Spacewatch[END_REF] estimate they were able to detect the motions of objects out to 1250 au although, as they stated, with their magnitude limit of ∼ 20.5 they can only detect Jovian sized objects at this distance. Schwamb et al. [START_REF] Schwamb | A Search for Distant Solar System Bodies in the Region of Sedna[END_REF] indicate that they were able to detect the motions of objects out to 1000 au, although their limiting magnitude of = 21.3 corresponds to Pluto only out to 165 au. After Figure 1: Minimum visible planet radius as a function of distance for four surveys: Schwamb et al. [START_REF] Schwamb | A Search for Distant Solar System Bodies in the Region of Sedna[END_REF] (blue), Holman et al. [START_REF] Holman | Primary results from the Pan-STARRS-1 Outer Solar System Key Project[END_REF] (magenta), Sheppard and Trujillo [START_REF] Sheppard | New Extreme Trans-Neptunian Objects: Toward a Super-Earth in the Outer Solar System[END_REF] (red), and this work (black). The solid lines represent the limit of the region of phase space which an object can be detected by the surveys.

The diagonal lines correspond to the limiting R band magnitude, these values are converted to radius by scaling Pluto's apparent magnitude (using Pluto's albedo). The shaded green area is the region of phase space that this work is sensitive to, with light green if there is overlap with other surveys, and dark green being parameter space unique to this study.

our current work began, two more surveys have been used to search for slowly moving objects. The Pan-STARRS data has been searched for objects out to 2000 au [START_REF] Holman | Primary results from the Pan-STARRS-1 Outer Solar System Key Project[END_REF]. The survey has a limiting magnitude of = 22.5, which would detect Pluto out to 250 au, and covered nearly the whole sky north of -30 in declination (excluding the galactic plane). Sheppard and Trujillo [START_REF] Sheppard | New Extreme Trans-Neptunian Objects: Toward a Super-Earth in the Outer Solar System[END_REF] searched a thousand square degrees and state sensitivity to objects out to 500 au; because multiple telescopes were used, their limiting magnitude varied from 24 to 25.5, with a majority of their observations having depths ≈ 24-24.6. Figure 1 shows the combinations of distance and object size that can be detected in the three of the surveys described above and in this work. In regards to detecting Pluto sized objects at distances greater than 300au, the surveys of Schwamb et al. [START_REF] Schwamb | A Search for Distant Solar System Bodies in the Region of Sedna[END_REF] and Holman et al. [START_REF] Holman | Primary results from the Pan-STARRS-1 Outer Solar System Key Project[END_REF] are not deep enough. Sheppard and Trujillo [START_REF] Sheppard | New Extreme Trans-Neptunian Objects: Toward a Super-Earth in the Outer Solar System[END_REF], on the other hand, would have been able to see Pluto sized objects out to almost 500 au, but only with a small fraction of their survey. Most of their survey could not see objects fainter than = 24.6, which is Pluto at 350 au.

In this paper we present the data set used (Section 2), details of our searching method and the results (Section 3), and how we turned the null result into an upper limit on the number of Pluto sized objects in the outer Solar System (Section 4).

Data

The data used for this work come from the Outer Solar System Origins Survey (OSSOS), designed to detect and track a large sample of TNOs in the 10-300 au distance range.

The survey covers a small fraction of the the ecliptic's area: ∼167 square degrees that is split up into eight, roughly equally sized, regions of sky known as blocks [START_REF] Bannister | OSSOS. VII. 800+ Trans-Neptunian Objects-The Complete Data Release[END_REF]. OSSOS' depth depends on the image quality (IQ) of the triplets (see next paragraph).Thus the limiting magnitude varies from block to block and ranges from = 24.5 to 25.2. The OSSOS observing cadence can be conceptually broken up into two parts, the imaging for discovery on one night ('triplets') and images for tracking, and thus orbit determination, taken on various other nights ('confirmation'). The triplet consists of three 287-sec images taken with 1-hour spacing, which were used to discover the TNOs using a movingobject detection software pipeline [START_REF] Petit | A highly automated moving object detection package[END_REF]. The confirmation images are single images taken at a variety of time intervals both before and after the triplet. The majority of the confirmation images reach deeper depths than the triplet images, either via a better IQ, longer exposure time, or a wider filter [START_REF] Bannister | OSSOS. VII. 800+ Trans-Neptunian Objects-The Complete Data Release[END_REF]. Most fields had a least one confirmation image taken in the a couple of days after the triplet, at least one a week after, at least one at ± one month, and one at ± two months. In some cases there were confirmation iamges that were ± three months from the triple. This cadence produced complete TNO orbital linkages; here we use the confirmation images for a different purpose (see below). The OS-SOS cadence also contains confirmation images taken in the following opposition, these confirmation images were only used in this work if a block was considered to contain too few confirmations in the discovery opposition. For a more complete understanding of OSSOS please refer to Bannister et al. [START_REF] Bannister | The Outer Solar System Origins Survey. I. Design and First-quarter Discoveries[END_REF] and Bannister et al. [START_REF] Bannister | OSSOS. VII. 800+ Trans-Neptunian Objects-The Complete Data Release[END_REF]

Method

Because we expect only a few Pluto-sized objects to be in the outer Solar System today and OSSOS only covered a small fraction of the ecliptic, we did not expect to find any objects in this search. Thus the goal of this work was to do a quick search to estimate a first upper limit on the number of distant Pluto-sized objects in the Solar System, to a factor of two to three accuracy. Thus, when in our data analysis we realised that it was possible to do something 'slightly better' but at a much larger time expense, we chose to mildly sacrifice precision.

To detect TNOs, OSSOS employed the commonly used method of searching for linearly moving objects in three shortcadence discovery triplet images. A TNO's on-sky rate of motion at opposition, in "/hour, can be approximated by 150∕ , where is the object's heliocentric distance in au. The original search set a lower limit of ∼0.5"/hour, which would comfortably detect motion in the triplet images. Motion slower than 0.5"/hour corresponds to objects beyond 300 au but resulted [START_REF] Bannister | The Outer Solar System Origins Survey. I. Design and First-quarter Discoveries[END_REF] in a rapidly increasing number of false positives due to stationary sources being flagged as moving due to centroiding jitters. OSSOS thus did not search these rates. In order to detect these (<0.5"/hour) Slow Moving Objects (SMOs) we use a different technique, searching for objects that appeared stationary in the triplet images, within some tolerance, but did not reappear in most of the confirmation images (some similarities to [START_REF] Brown | A Serendipitous All Sky Survey for Bright Objects in the Outer Solar System[END_REF]). This allows us to be sensitive to Pluto-scale and larger objects at great distance.

The first step of our algorithm is to create a catalogue of all the objects that appear stationary in each triplet. This was achieved by matching sources in the existing OSSOS source catalogues. Each triplet image has two source catalogues, one created using wavelets [START_REF] Petit | A highly automated moving object detection package[END_REF] and the other using S-Extractor [START_REF] Bertin | SExtractor: Software for source extraction[END_REF]. For an object to be classed as 'stationary' it needed to appear in all six catalogues of the triplets (2 catalogue creation methods for each of the 3 images). When matching sources from two different catalogues, the tolerance used was a weighted combination of the seeing on the two images and the distance an object moving at 0.5"/hour would have traveled. The seeing was used as a proxy for the uncertainty in the source position since the catalogues did not contain an estimate for these uncertainties.

We then identify all of the confirmation images where the (RA, Dec) sky position of a given stationary object is on the pixels of that confirmation image. This task was not trivial due to the slow drift in image position that OSSOS used to minimise TNO loss off the edges of the imaged sky areas. This necessitated a highly accurate absolute plate solution, which OSSOS already had. Each confirmation image that contained the desired (RA,Dec) is considered 'onpixels' for a particular stationary object. The catalogues for each on-pixels confirmation images are searched for a match to the stationary object. The seeing of the worst triplet image and the confirmation image, added in quadrature, were used as the tolerance for this search. If the stationary object was matched to a source in the on-pixels confirmation image catalogue, then the object was considered 'found' on that confirmation image. Each stationary object thus has a different number of potential detections on the full set of confirmation images.

Some of the confirmation images had poorer IQ than the triplet and thus the faintest stationary objects were not detected on all of its on-pixels confirmation images. Therefore we needed classify the stationary objects as either being bright, where the object should always be detected regardless of the seeing, or faint, where the object was below the mag limit on some fraction of the worst confirmation images. This boundary between the bright and faint was determined by simply examining graphs showing at which flux there was a drop off in average number of confirmation detections per stationary object (i.e. the average number of detections per stationary object is fairly constant for fluxes brighter than this boundary and steadily decreases as the flux decreases below it). For the OSSOS fields and depths, the ratio of faint to bright objects was approximately unity. We determined that this drop off simply starts when the object is too faint to be seen on the worst confirmation image, at which point the likelihood of finding these faint objects again in the confirmation image depends on a comfirmation image's seeing. If a faint stationary object was not found on a confirmation image whose (RA,Dec) is present, but that confirmation image's seeing was bad enough to fail a quality check, then that confirmation image is not counted as on-pixels for the stationary object. We assume that the bright objects should always be detected in the confirmation images, independent of the seeing. On average there were about 10 useful confirmation images per stationary object.

Any stationary object that did not reappear in any of the confirmation images, which would be the desired signal of a real SMO, were placed in a candidate list. To negate the possibility of a SMO not making it into the candidate list due to a chance cosmic ray or asteroid causing a false detection at that position on a confirmation image, stationary objects that were found on up to two confirmation images were included in the candidate list. The remaining objects had multiple detections and were considered 'confirmed' stationary objects.

All candidates were vetted by an operator looking at cutouts of the images centred on the candidate. In a rapid first pass, only the triplet images were visually examined to reject anything that was obviously not a point source. In a second pass, all of the images where a candidate is on-pixels were looked at (the triplet, and all confirmation images where that (RA,Dec) is available).

After applying this method to each field of each OSSOS block, no SMOs were found. The number of first pass candidates per square degree ranged from tens to a few hundred, with roughly a third of these candidates making it to the second pass. Almost all of the candidates were false positives, the exception being 66 detected supernovae (see Fig 2 for an example). These supernovae were at peak brightness near the time of the triplet, so they usually were not seen in the confirmation images before the triplet and only visible in a couple of the confirmation images taken a few days/weeks after. Thus not exceeding the maximum two detection over all confirmation images needed to still be a candidate.

The vast majority of false positives suggested for vetting were very faint stars or caused by halos of bright stars. That is, in the diffraction halo of bright stars local peaks in brightness can occur and the pipeline identifies these as (stationary) objects, or a faint source in a very good-seeing triple may be not get into the confirmation catalogs. In both these cases the nature of the candidate is obvious to the human operator. A rarer and interesting type of false positive are optical ghosts caused by internal reflections of very bright stars which then appear as faint sources with normal (or nearly normal) point-spread functions. The barely different pointings for each triple image caused the location of the optical ghost to move, but only barely perceptibly and thus less than the stationary tolerance for the triplets. For the confirmation images, however, the blocks shifted enough that the optical ghost is no longer anywhere near its position in the triplets. This mimics the signal that of a real SMO with the main difference being the usually non-linear movement of the optical ghosts in the triple. For the few cases where the non-linearity was less pronounced, we examined the projected position of the optical ghost in the confirmation images a few days later. Because the optical ghost had apparent rates of only a few tenths of an arcsecond per hour, their projected positions a day later were less than 10 arcseconds away from their triplet positions. If they were actually SMOs finding them in the confirmation image a couple of days later would have been trivial. None of the 'optical ghosts' re-appeared, thus proving that these signals were not SMOs. Over the entire survey, 26 optical ghosts were found.

Survey Simulator

Even though no SMOs were discovered, we can use this null result, along with the fact that initial OSSOS search did not find any nearby objects of this size, to place an upper limit on the number of large (Pluto-sized and bigger) TNOs in the outer Solar System, subject to some assumptions. Firstly we assume that the code would have found a real SMO, if there was one above the mag limits, since objects that behaved similarly to a SMO (optical ghosts) made it into the candidate list. Therefore no planting and finding of artificial objects was required to establish a magnitude detection limit, because we assume that the efficiency of the code to find a real SMO of a certain r-band magnitude is the same as that established for an OSSOS TNO in that same block [START_REF] Bannister | OSSOS. VII. 800+ Trans-Neptunian Objects-The Complete Data Release[END_REF], allowing us to use the OSSOS survey simulator, both of which rely on the detection efficiency of the triplet, as the recovery/confirmation rate is very high. This is an approximation, but good enough for our factor of 2 to 3 estimate.

The OSSOS survey simulator works by creating one object at a time from an input orbital and size distribution model and assessing whether this object would have been found by OSSOS. For more detail see Kavelaars et al. [START_REF] Kavelaars | The Canada-France Ecliptic Plane Survey L3 Data Release: The Orbital Structure of the Kuiper Belt[END_REF], Lawler et al. [START_REF] Lawler | OSSOS: X. How to use a Survey Simulator: Statistical Testing of Dynamical Models Against the Real Kuiper Belt[END_REF].

The orbital distribution we use for potential large semimajor axis objects consists of a uniform semi-major axis, , ranging from 150 au to 999 au. We assume that the pericentre distance, , distribution is uniformly distributed starting from = 37 au out to 99 au. The inclination distribution used is the typical sin times a Gaussian; because a SMO would be either a scattering or detached object and thus will be part of the hot population, we use a width of 13 • [START_REF] Petit | The Canada-France Ecliptic Plane Survey (CFEPS) High-latitude Component[END_REF]. All the other parameters (longitude of ascending node, the argument of perihelion, and the mean anomaly) are uniformly distributed from 0 to 360 • .

For the simulated size distribution, we wanted to examine objects ranging from the smallest object that we would have been able to detect up to a Mars-sized object. A Marssized object (with Pluto's albedo) would have an absolute magnitude, , of -3.

Known large TNO's have comparatively high albedos; if distant large TNOs objects were to have lower albedos then they would have to be larger in size for us to detect them (the product of albedo and reflecting area being constant).

The smallest object that we can detect would have an apparent mag of 25.5 at 300 au, corresponding to an object with ≈ 0.7. The matching tolerance used in making the stationary catalogue allowed the algorithm to find objects moving slightly faster than 0.5"/hour, due to the seeing of the triples. The closest object the algorithm deployed here could detect was actually slightly closer than 300 au. Due to this, and that the range would be a convenient 5 magnitudes, we decided to simulate objects down to = 2 (a range spanning 5 magnitudes corresponds to a change in radius by a factor of 10). Therefore the mag range we used was -3 to 2.

For the functional form of the absolute magnitude distribution of our simulated population, we look to known TNOs whose distribution is often represented with an exponential law of the form

(< ) ∝ 10 (1)
where N(< ) is the cumulative number of objects that have an absolute magnitude of ' ' or less and is the logarithmic slope. The value of is known to differ for different ranges. For objects brighter than of 6, the known TNOs exhibit two slopes with a transition at ∼ 3 (Figure 3). The values for are = 0.14 for the shallow slope and = 0.61 for the steep slope. The largest value in our desired range, = 2, corresponds to ∼ 2.5, which is lower than the apparent transition near 3. Thus the simulated sample is situated in the range where the distribution slope is shallow. Because there is no clear argument that the slope would change for TNOs larger than Pluto, we used a logarithmic size distribution with a slope of = 0.14 for the entire simulated population. . Two exponential functions are plotted (dashed lines) to guide the eye and match the slope of the data; note that these are not fits to the data. The logarithmic slope, , of each exponential function is displayed each line. The obvious roll-over beyond ∼ 6 is due to the increasing observational incompleteness of fainter TNOs. Data obtained from the Minor Planet Center.

To get a 95% upper limit from the survey simulator we need to estimate the population size needed so that the chance of getting no detections is < 5%. This corresponds to having an expected value of 3 simulated detections (for Poisson statistics, as -3 ≃ 5%). Therefore we ran the survey simulator until we got 3 detections, and the number of objects generated serves as an estimate of the 95% upper limit on the true intrinsic population of these large objects. We ran the simulator to get 1000 independent estimates for this upper limit (only the random seed changed). A histogram of the 1000 trials is shown in Figure 4. The sample has a median value of 1100. Although this value is model dependent, as stated earlier we were only looking for a factor of two to three accuracy, and we found that moderate changes in the parameters did not affect our conclusions.

While studying the survey simulation, we noted an interesting aspect of the observational biases. To study the distance distribution of detectable objects, we define a quantity , which we refer to as the fractional orbital distance, to measure how far beyond perihelion the objects were when detected.

= - - (2)
where is the object's heliocentric distance at detection, and and are the objects perihelion and aphelion distance, respectively. Thus moves smoothly from 0 to 1 as goes from to , and its distribution provides insight into the concentration of detection at perihelion or aphelion. Unsurprisingly, the intrinsic distance distribution for these highly eccentric objects (black line, left panel in Figure 5) has a peak at = 1 due to a long residence near aphelion caused <2) planetary scale bodies currently in the outer Solar System. The median of this distribution (dashed line) is taken to be our best estimate for the upper limit. by Kepler's second law. The small spike at perihelion (F=0) is due objects having close to zero radial motion and thus spend more time near the circle = (see Figure 6), even without detection bias. We then compare the distribution of the simulated detections for 3 different magnitude ranges (-3 < < -2, -1 < < 0, 1 < < 2). The smallest object range (dwarf planets) are predominantly found at low values (near perihelion) due to the fact that a vast majority of them are only above the magnitude limits when near perihelion. This phenomenon, that perihelion flux bias wipes out the aphelion spike in the distance distribution, is not new and was first illustrated in Jones et al. [START_REF] Jones | The CFEPS Kuiper Belt Survey: Strategy and presurvey results[END_REF]. In contrast the left panel in Figure 5 shows that the largest detected objects are more uniformly spread in detection (example Gerdes et al. [START_REF] Gerdes | Discovery and Physical Characterization of a Large Scattered Disk Object at 92 au[END_REF]) and in addition still maintain a strong detection spike at aphelion. This is simply because the Mars-scale objects can be detected further out, including the frequent case of being near aphelion. The implication is that past surveys with similar depths could have detected the flux from a Mars-sized object; at this size the most likely single case is being above the magnitude limit while near apocentre. Even though such an object would be visible, at hundreds of au away it was almost certainly below the survey rate cuts and would not be identified as a moving target and thus missed. However, most of the previous wide-field surveys searching for distant Solar System objects do not go to 24th magnitude, but should still be able detect (in terms of flux) a Mars-sized object out to few hundred au. According to Schwamb et al. [START_REF] Schwamb | A software roadmap for solar system science with the large synoptic survey telescope[END_REF] & Schwamb et al. [START_REF] Schwamb | Large synoptic survey telescope solar system science roadmap[END_REF] the current pipeline for detecting moving objects in Large Synoptic Survey Telescope (LSST) cannot detect the motion of objects beyond 200 au. Unless LSST include a search method, like ours, that examines multi-night data for objects that do not move perceptibly in a single night, they could miss a Mars-sized object near apocentre.

The fractional orbital distance is related to the true anomaly of course, but provides different insights. The right panel in The fraction of objects with a certain fractional orbital distance, F (left), and the true amonaly (right) for different magnitude ranges are red for -3 < < -2, green for -1 < < 0 and magenta for 1 < < 2. Each group has around 90,000 values which are split up into 15 bins. The intrinsic population (black line) is added for reference. The spike of the intrinsic population near F=0 is real and due the radial component of the heliocentric velocity being small. Note that a range of semi-major axes are represented here, allowing for a few of the even physically smallest (magenta-coded) objects to be detected near apocentre.

Figure 5 shows the true anomaly distribution for both the intrinsic population and for the simulated detections for the same three -magnitude ranges as the left panel; we only plot the true anomaly from 0 to since it is symmetric around . The intrinsic distribution nicely shows how this largepopulation spend more time at higher true anomaly due to Kepler's Second Law. It also shows how the detection bias eventually truncates the distribution at large-enough true anomaly, producing a detection maxima in the range of true anomaly 2 -2.5 (for these relatively large objects). These maxima correspond to the small bumps in the F distributions between = 0.1 -0.4 in the left panel of Figure 5. What the true anomaly plot hides is the increase in detections near perihelion, which is represented as the spikes at = 0 in the left hand plot, which is present even in the intrinsic distribution but is magnified in the detected sample. This occurs because while the time spent near a true anomaly of zero is indeed small, the time spent near ∼ is not (Figure 6). This perihelion spike (which is even more pronounced for lower eccentricity orbits) is an important phenomenon in flux-limited surveys if one is going to determine whether the distribution of detection distances matches a model because large swaths of true anomaly have nearly the same reflected flux, and it is the distance distribution that is thus critical. Gladman et al. [START_REF] Gladman | The Resonant Trans-Neptunian Populations[END_REF] clarifies how this is also affected by, and can thus help constrain, the absolute magnitude distribution.

Discussion & Conclusion

After searching through the ∼167 square degrees of the OSSOS data for a slow moving object beyond 300 au, 66 supernovae and 26 optical ghosts were found but no slowmoving solar system objects. By simulating high semi-major axis TNOs we obtain an understanding of the statistics of the objects we were sensitive to. Although this work is the first search sensitive to Mars-scale objects at 500-1000 au, the upper limit of ∼1000 objects from -3 < < 2 is not very constraining. Half of this distribution ( < -0.5) corresponds to Pluto-scale and larger objects. Estimates based on the fact that three such objects (Pluto, Eris and Triton) are currently known have been used to predict that ∼ 1000 -4000 must have existed in the very early Solar System during the planet migration phase (e.g. Nesvorný and Vokrouhlický [START_REF] Nesvorný | Neptune's Orbital Migration Was Grainy, Not Smooth[END_REF]), given an estimated 'retention efficiency' of order 10 -3 . Thus, a current upper limit of 1000 such bodies is not very constraining to these late-stage planetary formation models, as those models would indicate <10 such objects likely remain in the outer reaches of the Solar System. Our modeling does indicate, however, that if a few such objects still exist in the scattering or detached populations of the outer Solar System, they may very well have been near aphelion moving so slowly that previous deep ( ∼24-25) surveys would have been unable to detect them. LSST would need to alter their pipeline to be able to detect these extremely slow moving targets using their multi-night data. If we crudely scale from our 0.3% of detection to LSST, by saying that survey will cover 50 times the ecliptic sky area of OSSOS down to a similar depth, LSST has a 15% chance of finding a single (-3 < < 2) 'planet', if these objects are distributed in the scattering population roughly like as assumed here. Because the H-magnitude distribution is shallow, usage of large apertures is not as important as sky coverage; the sum of existing wide-field surveys (eg. Sheppard and Trujillo [21], Bernardinelli et al. [START_REF] Bernardinelli | Trans-Neptunian objects found in the first four years of the Dark Energy Survey[END_REF]), some of which is far from the ecliptic, provides an even smaller chance of success than LSST of finding such a distant planet.

Figure 2 :

 2 Figure2: Images of a supernova event (centre of the red circles) in the outskirts of a distant galaxy that was identified as a SMO candidate by our code, because it was only detected by the code on two (out of 24) confirmation images. The top row contains images taken 2 months (left) and 1 month (right) before the triplet. The three triplet images are in the middle row. The bottom row contains images taken a day (left), 1 month (middle) and 8 months (right) after the triplet. The sudden appearance and fading out on the timescale of a month is characteristic of a type 1a supernova. Each cut out is about 10" wide.

Figure 3 :

 3 Figure3: The cumulative heliocentric absolute visual magnitude distribution of the known TNOs down to = 8 (blue line). Two exponential functions are plotted (dashed lines) to guide the eye and match the slope of the data; note that these are not fits to the data. The logarithmic slope, , of each exponential function is displayed each line. The obvious roll-over beyond ∼ 6 is due to the increasing observational incompleteness of fainter TNOs. Data obtained from the Minor Planet Center.

FrequencyFigure 4 :

 4 Figure 4: A histogram constructed from the 1000 estimates of the 95% confidence upper limt on the population of large (-3<<2) planetary scale bodies currently in the outer Solar System. The median of this distribution (dashed line) is taken to be our best estimate for the upper limit.

Figure 5 :

 5 Figure5: The fraction of objects with a certain fractional orbital distance, F (left), and the true amonaly (right) for different magnitude ranges are red for -3 < < -2, green for -1 < < 0 and magenta for 1 < < 2. Each group has around 90,000 values which are split up into 15 bins. The intrinsic population (black line) is added for reference. The spike of the intrinsic population near F=0 is real and due the radial component of the heliocentric velocity being small. Note that a range of semi-major axes are represented here, allowing for a few of the even physically smallest (magenta-coded) objects to be detected near apocentre.

Figure 6 :

 6 Figure6: Schematic of an eccentric orbit (solid ellipse) that has been divided into segments of equal true anomaly. Dotted circles represent the perihelion and aphelion distances. Near perihelion, an object's heliocentric distance is relatively constant over a large range of true anomalies, producing a concentration of detections with ∼ (as demonstrated in Figure5)

Acknowledgements

This work was supported by funding from the National Sciences and Engineering Research Council of Canada.