ceo2 (111) electronic reducibility tuned by ultra-small ... · 1 ceo2 (111) electronic reducibility...

CeO2 (111) electronic reducibility tuned by ultra-small supported bimetallic Pt-Cu clusters

Lauro Oliver Paz-Borbóna*, Fernando Buendiaa, Ignacio L. Garzóna, Alvaro Posada-Amarillasb , Francesc Illasc, Jun Lid,e

aInstituto de Física, Universidad Nacional Autónoma de México, Apartado Postal 20-364, 01000 CDMX, México

bDepartamento de Investigación en Física, Universidad de Sonora, Blvd. Luis Encinas & Rosales, 83000 Hermosillo, Sonora, Mexico

cDepartament de Ciència de Materials i Química Física & Institut de Quı́mica Teòrica i

Computacional (IQTCUB), de la Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain

dDepartment of Chemistry, Tsinghua University, Haidian District, Beijing 100084, China

eDepartment of Chemistry, Southern University of Science and Technology, Shenzhen 518055,

Supporting Information

*Corresponding Author: oliver_paz@fisica.unam.mx

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.This journal is © the Owner Societies 2019

Periodic CeO2(111) surface model

Figure S1. Schematic diagram of the pristine (3x3) CeO2(111) surface used in this work. The location of O atoms on either top, bottom and interlayer sites is indicated. During our DFT calculations, the bottom O-Ce-O (CeO2) trilayer is kept fixed.

DFT-based Basin Hopping Monte Carlo (BH-DFT) global optimization approach for bimetallic clusters

Our BH-DFT global optimization tool [1,2] implemented for bimetallic PtmCun clusters supported on CeO2(111), starts by randomly placing a Pt atom across the xy slab plane, at an initial height (h) approximately 2.0 Å away from the CeO2(111) surface, see Figure S1. The next Pt atom is positioned according to the spherical coordinates notation: polar and azimuthal angles (θ,φ) are randomly generated according to a normal distribution between 0 and 2π; while the radial distance (r) value is randomly taken from a lower and upper Pt-Pt bond length range i.e. 1.50 Å to 2.50 Å. The next atom is placed at a new randomly generated (r,θ,φ) coordinates. Subsequent Pt atoms are placed by randomly selecting a previously generated Pt atom, which is now used as a starting point. Once all Pt atoms are randomly placed over the oxide CeO2(111) surface, the code proceeds to place the Cu atoms following a similar procedure as for the Pt ones. This leads to a “pseudo” spherical 3D-like initial PtmCun supported configuration, where metal atoms are placed at a distance no shorter than 2.0 Å. Flat (planar) structures can be enforced by constricting the z coordinate to a fixed distance (height) from the substrate. The same procedure applies to PtmCun gas-phase clusters.

Once the initial gas-phase or supported PtmCun cluster has been generated,

it undergoes a DFT relaxation to bring it to a local minimum (see Figure S1). For a converged structure, a move factor of 0.6 Å, multiplied by a normal random distribution between (-1, 1), is applied to the cluster xyz coordinates (move.py routine). This ensures that the random displacement (or “kick”) moves all PtmCun xyz coordinates in all random directions. This move highly disrupts the PtmCun cluster geometry, and it is the equivalent to escape from an attractive energy basin and to land in another area of the vast PES landscape at each Basin Hopping Monte Carlo (MC) step. In case the initial PtmCun structure does not electronically SCF converge, it is once more randomly generated and subjected to a DFT relaxation. After 10 BH-steps, an implemented atom-exchange routine (swap.py) allow us to search for low-energy permutations of atoms A and B (i.e. homotops). For example, for the case of a Pt3Cu2 cluster, the swap.py routine will select the 2 Cu atoms and exchange them for 2 randomly selected Pt atoms. This assure us to efficiently explore different chemical orderings and to cover wider bimetallic cluster PES areas than could be very difficult to reach using only random “kicks”.

Next, the MC criterion (e-ΔE/kT) is used in order to accept/reject relaxed

putative PtmCun minima configurations (both supported, and in the gas-phase). We use a fictitious temperature of 2500 K to increase the probability to accept higher energy PtmCun configurations. 100 MC steps are performed for both supported and gas-phase PtmCun clusters due to the computationally intensive BH-DFT searches involving DFT relaxations using an 81 atom (3x3) CeO2(111) surface. BH-DFT searches are initially performed with a low kinetic energy cut-offs of 20/180 Ry for both wave function and charge density to allow for a rapid PES scan of bimetallic

PtmCun supported clusters. After BH-DFT searches, energetically stable minima PtmCun configurations are further DFT relaxed using a higher wave function/charge density cut-off values (40/320 Ry).

[1] L. O. Paz-Borbón, A. López-Martínez, I. L. Garzón, A. Posada-Amarillas and H. Groenbeck, Phys. Chem. Chem. Phys., 2017, 19, 17845–17855. [2] https://github.com/andoresu47/Basin-Hopping

Figure S2. Basin Hopping Monte Carlo (BH-DFT) flowchart implementation for bimetallic clusters, both in the gas-phase and supported over the CeO2(111) surface. Simple random xyz moves (via the move.py routine) are applied to DFT relaxed PtmCun configurations using a “kick” factor of 0.6 Å. It is multiplied by a random number generated using a normal random distribution between (-1, 1) to allow atom displacements in all xyz directions. After 10 BH-steps, an atom-exchange routine (swap.py) allow us to efficiently search for low-energy permutations of atoms A and B (i.e. homotops).

PtN, CuN, and bimetallic PtmCun gas-phase clusters (N = m + n) up to 5 atoms

Table S1. Calculated properties for monometallic PtN, CuN clusters and bimetallic PtmCun gas-phase clusters (N= m + n), size range 2 – 5 atoms. Calculated system magnetization moment (MTot), number of metal-metal and intermetallic bonds – including average values in Angstroms (Å) – as well as calculated excess (ΔDFTPtCu) and binding energies (Ebin) are shown.

MTot (μB)

# of Pt-Pt

# of Pt-Cu bonds

# of Cu-Cu bonds

Pt-Pt (Å)

Pt-Cu (Å)

Cu-Cu (Å)

ΔDFTPtCu (eV)

Ebin (eV)

Pt2 2.00 1 0 0 2.361 0.0 0.0 0.0 1.77

Pt1Cu1 1.00 0 1 0 0.0 2.326 0.0 0.11 1.35

Cu2 0.07 0 0 1 0.0 0.0 2.266 0.0 1.05

Pt3 2.01 3 0 0 2.510 0.0 0.0 0.0 2.36

Pt2Cu1 1.00 1 2 0 2.478 2.443 0.0 -0.33 2.06

Pt1Cu2 0.09 0 2 1 0.0 2.385 2.457 -0.61 1.74

Cu3 1.01 0 0 3 0.0 0.0 2.399 0.0 1.13

Pt4 4.05 5 0 0 2.533 0.0 0.0 0.0 2.66

Pt3Cu1 1.04 3 3 0 2.579 2.533 0.0 -0.39 2.46

Pt2Cu2 0.02 1 4 1 2.588 2.482 2.552 -0.55 2.20

Pt1Cu3 0.90 0 3 3 0.0 2.472 2.418 -0.22 1.82

Cu4 0.06 0 0 5 0.0 0.0 2.388 0.0 1.47

Pt5 4.01 9 0 0 2.626 0.0 0.0 0.0 2.91

Pt4Cu1 3.02 5 4 0 2.587 2.593 0.0 -0.55 2.75

Pt3Cu2 2.03 2 6 1 2.548 2.525 2.515 -0.87 2.56

Pt2Cu3 1.04 0 6 3 0.0 2.461 2.524 -1.18 2.36

Pt1Cu4 0.08 0 3 6 0.0 2.472 2.454 -0.74 2.01

Cu5 1.00 0 0 7 0.0 0.0 2.398 0.0 1.60

MTot (μB)

Ce+4 to

Pt-Pt bonds

Pt-Cu bonds

Cu-Cu bonds

Pt-Pt (Å)

Pt-Cu (Å)

Cu-Cu (Å)

Pt-O bonds

Cu-O bonds

Pt-O (Å)

Cu-O (Å)

ΔDFTPtCu (eV)

Eads (eV)

Pt1 2.00 1 0 0 0 0.0 0.0 0.0 2 0 2.008 0.0 0.0 3.04

Cu1 1.00 1 0 0 0 0.0 0.0 0.0 0 2 0.0 2.048 0.0 2.60

Pt2 2.00 1 1 0 0 2.435 0.0 0.0 2 0 1.903 0.0 0.0 2.91

Pt1Cu1 1.00 1 0 1 0 0.0 2.425 0.0 1 1 1.916 1.845 -0.13 2.58

Cu2 0.00 1 0 0 1 0.0 0.0 2.356 0 2 0.0 1.824 0.0 1.79

Pt3 0.00 0 2 0 0 2.514 0.0 0.0 3 0 1.950 0.0 0.0 2.68

Pt2Cu1 1.00 1 1 2 0 2.535 2.515 0.0 2 1 1.930 1.869 -0.59 3.22

Pt1Cu2 2.00 1 0 2 1 0.0 2.448 2.453 1 2 1.955 1.842 -0.14 2.78

Cu3 0.90 1 0 0 3 0.0 0.0 2.359 0 3 0.0 1.843 0.0 3.54

Pt4 0.00 0 4 0 0 2.586 0.0 0.0 4 0 1.970 0.0 0.0 3.40

Pt3Cu1 1.00 1 2 3 0 2.533 2.548 0.0 3 1 1.951 1.904 -0.62 3.70

Pt2Cu2 2.00 1 1 3 1 2.495 2.521 2.551 2 2 1.951 1.860 -0.20 3.20

Pt1Cu3 1.00 1 0 3 2 0.0 2.482 2.455 1 3 1.989 1.866 -0.34 3.76

Cu4 0.00 2 0 0 5 0.0 0.0 2.415 0 4 0.0 1.843 0.0 3.71

Pt5 0.00 0 5 0 0 2.640 0.0 0.0 7 0 2.068 0.0 0.0 3.22

Pt4Cu1 1.00 2 4 2 0 2.597 2.531 0.0 5 1 2.017 1.900 -0.09 2.94

Pt3Cu2 0.00 2 2 3 1 2.661 2.510 2.619 4 2 1.966 1.875 -0.35 3.05

Pt2Cu3 1.00 2 1 3 3 2.595 2.496 2.590 1 4 1.929 1.925 -0.29 2.84

Pt1Cu4 2.00 2 0 2 5 0.0 2.492 2.430 1 3 1.988 1.845 0.12 3.04

Cu5 3.00 3 0 0 7 0.0 0.0 2.486 0 6 0.0 1.870 0.0 4.07

Table S2. Calculated properties for monometallic PtN, CuN clusters and bimetallic PtmCun clusters (N= m + n) supported on CeO2(111), size range 1 – 5 atoms. Calculated system magnetization moment (MTot), number of reduced Ce4+ to Ce3+ atoms, number of metal-metal and intermetallic bonds – including average values – as well as calculated excess (Δ) and adsorption energies (Eads) are shown.

XYZ coordinates Putative global minima PtN gas-phase clusters Pt2 Pt 1.394139795 6.248816477 3.931587905 Pt 0.246540193 4.559125941 5.116125357 Pt3 Pt 7.374835935 4.199665593 7.649287920 Pt 7.654097847 2.440409841 9.417152069 Pt 9.323298433 2.620176526 7.552580019 Pt4 Pt 3.311704959 3.409589474 6.719802944 Pt 1.684022326 5.563758238 3.412948363 Pt 3.719311159 5.001814822 4.798576458 Pt 1.699010785 3.434152629 4.775654098 Pt5 Pt 7.137581796 7.305433025 2.565178681 Pt 7.210141262 9.247386722 4.364961702 Pt 5.777429276 7.141254282 4.822812231 Pt 4.873391272 9.503641799 5.583911752 Pt 5.036925974 8.850073494 3.024477919

Putative global minima CuN gas-phase clusters Cu2 Cu 3.751742978 2.815579567 3.607303199 Cu 3.091618506 4.427401465 5.056605991 Cu3 Cu 5.694194200 7.122651691 1.847386587 Cu 3.507955582 6.884598285 2.604936452 Cu 5.256076700 8.351792612 3.758843361 Cu4 Cu 9.181164567 8.924324828 4.659178062 Cu 7.069272962 9.039450641 3.755993694 Cu 8.624975123 10.807096959 3.254814470 Cu 7.618347085 7.157831365 5.156649835 Cu5 Cu 8.245153809 9.617210954 4.634062167 Cu 10.238501155 9.131585300 3.376849891 Cu 10.186276622 7.436611004 1.711409082 Cu 10.306192628 10.730762345 5.134931785 Cu 8.169993079 7.968992790 2.864576329

Putative global minima Ptm-Cun gas-phase clusters Pt1Cu1 Pt 6.984617337 4.117963016 5.437205578 Cu 7.900311482 6.007082587 6.437763746 Pt1Cu2 Pt 6.919821532 6.162542666 2.843054022 Cu 5.125671018 4.683238363 3.378666605 Cu 4.801481655 7.119205501 3.374533808 Pt1Cu3 Pt 3.464741006 11.149840579 -2.798481581 Cu 4.135692037 9.386830004 -4.405760088 Cu 2.809626728 8.797973902 -2.467511372 Cu 1.824471890 10.056853847 -4.291354151 Pt1Cu4 Pt 1.958692109 5.132429500 9.315844414 Cu 3.957883038 4.547039713 7.985588445 Cu 2.718599166 6.588604697 7.470463440 Cu 4.041062250 6.449312366 9.522573013 Cu 5.174981404 6.583977206 7.334434846 Pt2Cu1 Pt 2.654541037 1.137342346 3.966623138 Pt 3.176602433 0.986974605 1.548873843 Cu 3.429572679 3.104115972 2.740925900 Pt2Cu2 Pt 15.537135721 6.754008304 2.117304480 Pt 15.496150273 8.103117008 4.325198482 Cu 13.572581131 6.697627204 3.630868073 Cu 14.177971954 8.821032012 2.352079711 Pt2Cu3 Pt 9.181494637 5.916663275 6.380400783 Pt 10.220750662 2.263028102 5.238466518 Cu 10.393262162 3.890242048 7.070285247 Cu 8.289268926 3.726098498 5.681479745 Cu 10.397171348 4.649008949 4.659570970 Pt3Cu1 Pt 5.602016421 7.837195291 6.845279945 Pt 4.163663353 6.878272070 4.928673382 Pt 5.988653530 8.626189008 4.422156685 Cu 3.892438930 9.289804134 5.675667071

Pt3Cu2 Pt 13.339892289 2.171548162 6.466835777 Pt 14.497054157 1.947845612 8.724866441 Pt 13.352725375 4.632272316 5.803129334 Cu 13.091848006 3.978766736 8.220545648 Cu 15.304561368 3.667398061 7.065692283 Pt4Cu1 Pt 5.085327296 12.608725097 4.610255261 Pt 4.785904639 8.811101173 3.054758585 Pt 6.469484781 10.497958017 4.051498168 Pt 4.102736139 10.264590952 5.079015456 Cu 4.350963809 11.254239030 2.616846341

Putative global minima PtN / CeO2(111) supported clusters Pt1 / CeO2(111) O -0.005049259 0.004185123 3.156028877 O -1.952373907 3.367234521 3.166719651 O -3.888376754 6.737867324 3.147011375 O 3.897978280 -0.002816202 3.149151586 O 1.948855391 3.358787705 3.159713104 O -0.000294526 6.752978510 3.151889564 O 7.790337300 0.019708136 3.177497823 O 5.860369626 3.359692186 3.139295252 O 3.890364769 6.750551464 3.167169717 O 0.116977132 2.310028771 6.384441105 O -1.927697684 5.600401355 6.309293637 O -3.880398929 9.006869630 6.380344805 O 3.782170660 2.253557417 6.394169358 O 2.034329937 5.589945099 6.277743427 O -0.019072466 9.018085398 6.338840260 O 7.815695231 2.241897318 6.336013522 O 5.767346703 5.610175813 6.404214691 O 3.839117729 8.985579703 6.411403167 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O 0.004578275 0.156109309 8.015555418 O -1.940690566 3.377982221 7.937461363 O -3.766882046 6.642791699 7.980365730 O 3.880497430 0.002301686 7.974845608 O 1.792425098 3.607504656 8.385369926 O -0.061267385 6.789352691 7.908679659 O 7.724944713 0.042013070 7.979663324 O 5.860413629 3.311738280 7.907062000 O 3.575624459 6.879290579 8.460924778 O 1.946553745 1.090434349 4.777814830 O 0.003308731 4.504425232 4.771070338 O -1.956023797 7.867130333 4.782653761

O 5.809735837 1.151694804 4.809426143 O 3.948532363 4.446269213 4.718998947 O 1.927952081 7.885798156 4.788356450 O 9.782215642 1.131106561 4.828215136 O 7.762230515 4.515688953 4.801495307 O 5.842674008 7.866033982 4.772524623 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.924495403 1.037307054 7.169550707 Ce -0.021038510 4.551015619 7.157388421 Ce -1.965675392 7.857675557 7.150828251 Ce 5.844276676 1.104395268 7.168176732 Ce 4.018435889 4.390094824 7.022097939 Ce 1.876016290 7.928145409 7.178229801 Ce 9.742414438 1.150190688 7.168106758 Ce 7.826349858 4.495463942 7.151514330 Ce 5.853482870 7.896994477 7.268871713 * Reduced Ce4+ to Ce3+ Ce 0.018917442 2.252683284 3.981587737 Ce -1.937296071 5.620462059 3.959255621 Ce -3.906761694 8.979731712 3.970683944 Ce 3.887919977 2.223445809 3.940039865 Ce 1.949139273 5.626874599 3.973516156 Ce 0.000616966 8.992221364 3.964986828 Ce 7.786956565 2.255504971 3.974574837 Ce 5.847928697 5.637436984 3.960093048 Ce 3.900291065 8.986996164 4.003937827 Pt 2.491058197 5.340348098 9.140452246

Pt2 / CeO2(111) O -0.012810367 -0.005589056 3.180001157 O -1.938001346 3.361112712 3.154416324 O -3.883275127 6.748073386 3.135454719 O 3.892796561 -0.001140235 3.151616754 O 1.943571947 3.370612336 3.168753207 O 0.003352882 6.746707386 3.147426680 O 7.781642047 -0.007683134 3.179104089 O 5.845051244 3.367819202 3.171789093 O 3.883804456 6.759849096 3.132807472 O 0.028649817 2.226103213 6.317385038 O -1.912904722 5.633796142 6.347236729 O -3.939414099 8.967750444 6.287005046 O 3.800007507 2.407013687 6.385434332 O 1.929801067 5.512256456 6.395490744 O 0.003480681 8.902673073 6.348683205 O 7.747736223 2.356571733 6.448025039 O 5.911245719 5.484843068 6.412990027 O 3.928559994 9.000852180 6.289487265 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O -0.011808610 -0.049920450 7.942202321 O -1.833620753 3.385698711 7.939844528 O -3.847914886 6.812095378 7.926374853 O 3.742098133 -0.110203325 7.939772696 O 1.429725924 3.023524422 8.418512800 O 0.014574747 6.710690536 7.979307896 O 7.914436223 -0.104437230 7.952941895 O 7.215881095 3.927051827 9.331984221 O 3.915546686 6.800255507 7.854813781 O 1.969178775 1.105927433 4.777810137 O -0.008764454 4.504054085 4.777243984 O -1.952945356 7.864593143 4.768431798 O 5.815036714 1.115400749 4.778696541 O 3.907829734 4.567946454 4.696872876 O 1.951203872 7.819985251 4.806763996 O 9.689944954 1.153470697 4.817337048

O 7.826661598 4.516911864 4.745207288 O 5.835935292 7.790930350 4.789160962 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.913660125 1.026528276 7.150771697 Ce -0.056241488 4.512936688 7.167416017 Ce -1.952511551 7.858483776 7.147907617 Ce 5.819432891 0.992506966 7.185001433 * Reduced Ce4+ to Ce3+ Ce 3.913957601 4.669844121 6.981367607 Ce 1.947966813 7.870394710 7.152978869 Ce 9.731785270 1.105834331 7.147990413 Ce 7.941928900 4.548735068 7.214296785 Ce 5.862880678 7.879496349 7.126580548 Ce -0.002325645 2.248536952 3.974691072 Ce -1.940325924 5.613310437 3.945626775 Ce -3.887811155 8.985905312 3.949492946 Ce 3.887327259 2.244392682 3.986988029 Ce 1.927559499 5.621614544 3.933661270 Ce -0.005890113 8.990115159 3.965220583 Ce 7.773993745 2.263229563 4.003433394 Ce 5.878569138 5.614040518 3.935180993 Ce 3.885201911 8.978525242 3.965068673 Pt 5.450771262 3.316237807 9.180496316 Pt 3.030605398 3.441109330 9.416316743

Pt3 / CeO2(111) O -0.024056734 -0.008835111 3.159710149 O -1.960251285 3.377436374 3.140461083 O -3.884581694 6.732443892 3.146537000 O 3.913044751 -0.008335350 3.155082727 O 1.950610864 3.393034947 3.157765831 O 0.020124371 6.758747984 3.176847614 O 7.786614846 0.001599087 3.174093624 O 5.845991353 3.373354841 3.148449982 O 3.901526755 6.744172600 3.164908057 O 0.026599391 2.260759865 6.340127779 O -1.930741380 5.634223314 6.334704684 O -3.869412148 9.031828531 6.420858769 O 3.800455640 2.232792862 6.354756846 O 1.931238103 5.562699478 6.281638410 O 0.030377620 8.983097775 6.282816246 O 7.753532072 2.254371331 6.356939136 O 5.848048311 5.593032879 6.376749029 O 4.033509217 9.092000109 6.439257207 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O -0.399733994 -1.460731949 9.224076645 O -1.990453366 3.410596227 7.925479850 O -3.821879477 6.643649743 7.974355908 O 4.736767309 -0.582463114 8.523783805 O 1.864718645 4.033841412 8.410994455 O 0.049435413 6.718532281 7.904601926 O 7.794387408 0.020023583 7.925373972 O 5.832414313 3.368062182 7.951809678 O 3.818238353 6.656145521 7.861302266 O 1.929610033 1.108564156 4.620019487 O -0.030156356 4.492352707 4.756025533 O -1.962668260 7.865812212 4.794153136 O 5.823325355 1.149628560 4.808331436 O 3.929483715 4.485900170 4.788286595 O 2.027825383 7.881655387 4.837344808 O 9.712439556 1.164690444 4.785809312

O 7.789324386 4.499095052 4.789303363 O 5.870264481 7.844701808 4.785448776 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.904430210 1.100834013 6.875428864 Ce -0.059038937 4.565297569 7.117089141 Ce -1.874926533 7.796878505 7.214210422 Ce 5.881756434 1.089857746 7.221833654 Ce 3.936896006 4.510116226 7.152772284 Ce 1.983195899 7.861919876 7.139767029 Ce 9.610273040 1.210536708 7.144988247 Ce 7.773190865 4.498455643 7.161749195 Ce 5.865796398 7.741709296 7.285779721 Ce -0.032477143 2.272044919 3.925471514 Ce -1.943332144 5.631688089 3.958695346 Ce -3.885269751 8.945295934 3.949543690 Ce 3.917119130 2.256602125 3.940402571 Ce 1.961869148 5.618833440 3.964683134 Ce 0.007160161 9.000302192 3.971534151 Ce 7.768720042 2.249258862 3.958244793 Ce 5.843036221 5.627121827 3.969869693 Ce 3.929721540 8.996604514 4.002158016 Pt 3.314525215 0.673788470 9.103461828 Pt 1.507656572 2.418797180 9.429489364 Pt 0.090682693 0.392998445 9.089679474

Pt4 / CeO2(111) O 0.003345891 -0.002413645 3.154913368 O -1.969799059 3.345718985 3.173906936 O -3.876485421 6.730749240 3.144794830 O 3.896523792 -0.001403193 3.147809776 O 1.932220845 3.343840788 3.147972281 O -0.019716368 6.746631511 3.154608086 O 7.762601306 0.021399682 3.164748446 O 5.872729428 3.358515210 3.188680006 O 3.894695674 6.768752453 3.148624429 O 0.011328100 2.224838752 6.247511412 O -1.771947216 5.636978280 6.477584370 O -3.883623134 8.976011380 6.440149197 O 3.848933318 2.405073739 6.389924041 O 1.887725289 5.641685922 6.268712598 O -0.018753102 8.911686758 6.422133878 O 7.760349498 2.262400788 6.302802267 O 5.770573565 5.595766771 6.377952053 O 3.891733440 8.816506263 6.398055466 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O -0.042681439 0.059635241 7.882703859 O -1.936584372 3.279798219 7.918746129 O -3.849153406 6.630177530 7.953151969 O 3.889230460 0.121091180 7.952671161 O 1.227343694 2.767660021 8.543870638 O -0.821022523 7.451138928 9.051467060 O 7.798062040 0.028295594 7.893074338 O 6.437295415 3.046987550 8.429976959 O 5.113916349 7.535120614 9.248384109 O 1.985499608 1.086198292 4.793703887 O -0.021976163 4.461992546 4.734267326 O -1.966808612 7.860525659 4.781472591 O 5.778960948 1.092488917 4.854633557 O 3.879050799 4.525027851 4.598063783 O 1.918427358 7.903883084 4.726131687 O 9.719743108 1.048453864 4.819833721

O 7.832697910 4.561851758 4.853332848 O 5.879873379 7.858989411 4.756087281 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.917072560 1.055385166 7.194658326 Ce -0.076054867 4.296379573 7.120902340 Ce -2.017609165 7.914211119 7.313820804 Ce 5.834418701 1.120091381 7.224457146 Ce 3.846675335 4.601468922 6.838833241 Ce 1.916342594 8.024283472 7.049201118 Ce 9.733950175 1.082472244 7.139172328 Ce 7.874087769 4.495094178 7.211597359 Ce 5.930090740 7.883102186 7.309899680 Ce -0.000570624 2.223692365 3.930963448 Ce -1.936600820 5.625151512 3.993602737 Ce -3.884438751 8.971309753 3.982388013 Ce 3.883890089 2.221691278 3.955804058 Ce 1.895896046 5.631346138 3.912973093 Ce -0.034468659 8.995507683 3.967762163 Ce 7.778303814 2.237487903 3.981284709 Ce 5.882834493 5.652435790 3.946303661 Ce 3.910907615 8.965123679 3.956226426 Pt 4.850687170 3.991483767 9.195704743 Pt 2.290911369 4.291225771 9.237953605 Pt 3.377235811 6.647013114 9.198510771 Pt 0.774621151 6.343776314 9.158039934

Pt5 / CeO2(111) O -0.032791931 0.002960786 3.176776989 O -1.936032404 3.354405435 3.144879387 O -3.878638360 6.747731297 3.147843892 O 3.898253678 -0.012087454 3.165649542 O 1.917626771 3.390723830 3.134668602 O 0.014108927 6.742219510 3.152151259 O 7.792761803 -0.034607006 3.163051239 O 5.859460923 3.364042211 3.156135217 O 3.874225119 6.780433287 3.170981218 O -0.062877448 2.190683341 6.300488845 O -1.921384338 5.604244982 6.449911863 O -3.791739244 9.139330811 6.272445932 O 3.912452482 2.270529985 6.269626042 O 1.982840945 5.531424910 6.409221414 O -0.102987639 9.016417617 6.444146708 O 7.687765609 2.314101505 6.420787644 O 5.850949450 5.504828279 6.223511269 O 3.930896181 8.967010652 6.378502861 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O -0.003141689 -0.070504628 8.173776199 O -1.950123069 3.277227328 7.960057577 O -3.870143321 6.772601948 7.784053399 O 3.740299383 -1.307477415 9.395090154 O 1.214529603 3.226966064 8.445429362 O 0.099651503 6.743887208 7.974701549 O 7.842741257 -0.048696115 7.910430604 O 7.009290944 4.327128841 9.403550742 O 3.957841753 6.790950155 8.115443793 O 1.921387401 1.195017095 4.715866710 O -0.012055357 4.504350879 4.803146168 O -1.919171220 7.818689792 4.787639876 O 5.873918971 1.087152067 4.730531157 O 3.870297084 4.511364140 4.646343479 O 1.902718617 7.849952922 4.881363275 O 9.653044723 1.123602785 4.837409195

O 7.857128777 4.489274091 4.756201750 O 5.871765164 7.863889357 4.799993130 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.815463077 1.237958742 7.063611375 Ce -0.091391867 4.505493429 7.215124906 Ce -1.946321531 7.812165086 7.257639793 Ce 5.968525503 1.044077458 7.041195367 Ce 3.921722860 4.565990468 6.924525432 Ce 1.939618950 7.833712595 7.208098796 Ce 9.700634046 1.121343659 7.186129475 Ce 7.852986484 4.531757703 7.283548461 Ce 5.887894797 7.862356551 7.114589395 Ce -0.023740397 2.255053480 3.935513153 Ce -1.947595665 5.614571918 3.979953383 Ce -3.872913170 8.999253054 3.970502840 Ce 3.887793588 2.241554751 3.931529030 Ce 1.917035028 5.617095346 3.945184913 Ce -0.012827724 8.961699781 3.963359436 Ce 7.791626308 2.263954903 3.957100683 Ce 5.883677140 5.619715378 3.923431258 Ce 3.884006486 8.986430876 3.981726281 Pt 4.015089117 0.698233799 9.142580315 Pt 1.783154687 -0.704874776 9.101925040 Pt 5.355527444 5.534890871 9.078392401 Pt 5.656829244 2.774535648 9.242070767 Pt 3.099101399 3.084044909 9.127575742

Putative global minima CuN / CeO2(111) supported clusters Cu1 / CeO2(111) O 0.016913725 -0.011449584 3.149726370 O -1.937071111 3.382812792 3.151892654 O -3.890386169 6.763689949 3.163772372 O 3.871752935 -0.015160848 3.160797978 O 1.945442704 3.361824852 3.148794006 O -0.003996524 6.740575883 3.149715209 O 7.776813052 -0.017329971 3.152430516 O 5.833923731 3.370492130 3.159203323 O 3.897371146 6.742852971 3.148583153 O -0.076932684 2.297662214 6.355470096 O -1.904348015 5.542705596 6.395236505 O -3.895760224 8.984580264 6.325374726 O 3.915347338 2.221177902 6.392205654 O 1.916953658 5.625147106 6.381370603 O 0.084288343 8.980503538 6.398350475 O 7.775986594 2.244294728 6.209329341 O 5.867228277 5.606409174 6.391466275 O 3.799029170 9.024058233 6.357151383 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O 0.014236116 -0.015729337 7.910049733 O -2.220847060 3.208916180 8.178211251 O -3.856720361 6.782381747 7.945407261 O 3.868471866 -0.057994428 7.943375722 O 1.805390174 3.296080753 8.001800597 O 0.012698758 6.725448177 7.987634919 O 7.776733334 0.318739317 8.184965062 O 6.129699219 3.199088221 8.198784604 O 3.874668561 6.892094047 7.998539754 O 1.928086570 1.144998170 4.811833473 O 0.022439082 4.501203690 4.781924886 O -1.917752831 7.846996153 4.826618942

O 5.800894865 1.086671442 4.754179945 O 3.885834242 4.493782501 4.766733609 O 1.947113891 7.833303825 4.781247952 O 9.756391288 1.105110514 4.731494765 O 7.793292752 4.536566153 4.755738949 O 5.804695621 7.866751689 4.812569174 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.926723530 1.111236571 7.155015249 Ce 0.048786176 4.502912969 7.163813698 Ce -1.945442990 7.857362678 7.175182771 Ce 5.795296934 1.089713470 7.117898151 Ce 3.875909004 4.495499663 7.251135561 * Reduced Ce4+ to Ce3+ Ce 1.958205513 7.804152938 7.162502830 Ce 9.739163505 1.115213644 7.097396339 Ce 7.788883286 4.533306949 7.119570474 Ce 5.834067654 7.879169596 7.154865127 Ce -0.003100726 2.252169547 3.960583677 Ce -1.935360989 5.616635121 3.969076408 Ce -3.894766797 8.987513616 3.971495892 Ce 3.888239298 2.252392341 3.981518497 Ce 1.959407614 5.606444655 3.970965544 Ce 0.004340085 8.974560165 3.968763271 Ce 7.779583178 2.246687983 3.950859346 Ce 5.828305419 5.614361138 3.984178396 Ce 3.882947667 8.983845145 3.961392288 Cu 7.775124338 2.230990644 8.927986694

Cu2 / CeO2(111) O 0.000922444 0.010487942 3.153613744 O -1.951101789 3.369697592 3.156164000 O -3.887240553 6.738004326 3.165203318 O 3.890897385 0.005324579 3.154835707 O 1.950320352 3.368554465 3.155260736 O 0.000510300 6.745787969 3.146902273 O 7.787404099 0.004201730 3.154446614 O 5.837670874 3.373602214 3.158016935 O 3.887864700 6.737604698 3.165579615 O 0.002500817 2.300703425 6.321511157 O -1.933772605 5.611124662 6.314091902 O -3.824401838 9.003888075 6.362428526 O 3.888207913 2.232672610 6.345970984 O 1.928258114 5.608096899 6.310595672 O 0.002225651 9.014243706 6.328424932 O 7.791212628 2.231290575 6.341918255 O 5.834474898 5.590923842 6.384297228 O 3.830487191 9.007657723 6.367484071 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O 0.007707096 0.179101957 7.969134526 O -1.958139863 3.373597820 7.945005791 O -3.623085719 6.643624624 8.092919008 O 3.934039355 0.006036605 7.990648261 O 1.960416053 3.374823231 7.948009752 O -0.001830360 6.773997091 7.940961524 O 7.742058376 0.010598197 7.992823999 O 5.842589435 3.330717895 7.964124794 O 3.595316911 6.633126041 8.102210227 O 1.941724882 1.125021857 4.789366364 O -0.001438112 4.504403275 4.762153512 O -1.926910732 7.873110849 4.773233941 O 5.839103687 1.130738391 4.780873326 O 3.894368481 4.481410327 4.783994968 O 1.931103317 7.872787901 4.774651402 O 9.737918694 1.125651486 4.788634323

O 7.778434672 4.482571183 4.783445264 O 5.838569167 7.883067268 4.724048845 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.944419169 1.147973825 7.150109939 Ce -0.000902916 4.507054625 7.107968330 Ce -1.879721862 7.904600630 7.129715405 Ce 5.840418952 1.123742591 7.171999459 Ce 3.877276769 4.432053578 7.111461230 Ce 1.885376491 7.904252504 7.131922415 Ce 9.735942415 1.144825098 7.149233014 Ce 7.794017332 4.428869982 7.107450527 Ce 5.852321779 7.974557253 7.101390080 * Reduced Ce4+ to Ce3+ Ce 0.000840954 2.250482419 3.959030807 Ce -1.942900281 5.622011052 3.959030990 Ce -3.885337583 8.993647777 3.962651146 Ce 3.894041099 2.242911967 3.958430743 Ce 1.942801229 5.621897991 3.959151972 Ce 0.001815027 8.995472238 3.947737118 Ce 7.782380744 2.242041402 3.956884197 Ce 5.837009975 5.621330755 3.979202349 Ce 3.887858809 8.993777605 3.965519020 Cu 7.026420629 6.523370890 9.594798845 Cu 4.670822001 6.561789679 9.573959410

Cu3 / CeO2(111) O -0.005436919 0.014603579 3.163552924 O -1.940259306 3.374103130 3.150714875 O -3.876975248 6.732260439 3.165589755 O 3.890148280 -0.007185056 3.153117819 O 1.933085924 3.377700305 3.141892572 O 0.001539664 6.735104982 3.149444096 O 7.793167948 -0.004211882 3.159618089 O 5.844919951 3.376039625 3.151967942 O 3.876220577 6.739415439 3.161364576 O 0.017091880 2.242432555 6.322494480 O -1.937705988 5.600797305 6.389914435 O -3.954284743 9.011893086 6.284765050 O 3.952098803 2.217035704 6.376269621 O 1.966004001 5.606724304 6.319426840 O 0.037722876 9.100513227 6.423468738 O 7.707182649 2.169922709 6.422274880 O 5.789612649 5.648990231 6.284745918 O 3.928424789 8.967799572 6.296134865 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O -0.005358094 0.033220872 7.970588796 O -1.854230909 3.306897223 7.985909673 O -3.988380041 6.777388843 7.986228074 O 3.508225859 -0.108959312 8.181063449 O 1.938010285 3.379911861 7.949581150 O 0.113352596 6.684482855 7.982419508 O 8.209755173 -0.244116363 8.217815432 O 5.765171747 3.751470604 8.176889928 O 3.867738536 6.728728473 7.968803873 O 1.964586470 1.156561892 4.769849998 O -0.002558947 4.498579441 4.790743765 O -1.909501973 7.859243355 4.788629054 O 5.833246275 1.127827243 4.673600305 O 3.874098779 4.463209447 4.767488061 O 1.914659072 7.861918623 4.797625524 O 9.716740422 1.154193511 4.799156506

O 7.803727593 4.467067754 4.791198564 O 5.838701343 7.859708647 4.738712543 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.873871746 1.126082734 7.141695328 Ce 0.017332299 4.485912103 7.172858592 Ce -1.981807612 7.814459124 7.192392608 Ce 5.816910002 1.138794621 6.900730885 * Reduced Ce4+ to Ce3+ Ce 3.855946901 4.554388687 7.138577245 Ce 1.986951330 7.799711286 7.170541621 Ce 9.806187419 1.124171963 7.173120132 Ce 7.810233296 4.553472985 7.184119479 Ce 5.839394046 7.861855988 7.113063727 Ce -0.001218161 2.251376724 3.956390262 Ce -1.944814418 5.618208240 3.977002279 Ce -3.890560755 8.987893845 3.966852846 Ce 3.865039803 2.262786891 3.928677365 Ce 1.942624792 5.618137947 3.955235598 Ce 0.000848221 8.956157569 3.946741901 Ce 7.812572479 2.262985878 3.945894416 Ce 5.837969973 5.615950105 3.964308387 Ce 3.892242510 8.988289474 3.963998048 Cu 5.847595991 2.473457310 9.503537948 Cu 4.664571533 0.447257319 9.500899022 Cu 7.028064722 0.422093317 9.466021189

Cu4 / CeO2(111) O -0.011802558 0.008205215 3.145722044 O -1.939362823 3.379411168 3.143798362 O -3.892122045 6.741167930 3.158888777 O 3.873478215 -0.016637684 3.159874069 O 1.935052035 3.371897301 3.156949048 O 0.002072996 6.735506437 3.155406161 O 7.801917125 -0.013826642 3.161230697 O 5.845802264 3.391108719 3.156060865 O 3.872122883 6.743970534 3.158884857 O 0.023236202 2.276336630 6.368266696 O -1.909263102 5.605506519 6.349463218 O -3.943854126 8.955720331 6.273385631 O 3.833299134 2.165266126 6.366295253 O 1.878576890 5.605543004 6.409062485 O -0.006074075 8.968145571 6.406377540 O 7.831270979 2.258250506 6.362826188 O 5.890826113 5.700818348 6.292685203 O 3.856980792 9.042270266 6.313581913 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O -0.026733299 0.002122985 7.937057759 O -1.886230668 3.390742057 8.001385653 O -3.844096298 6.739888438 7.964508916 O 3.405522267 -0.361031663 8.235211012 O 1.864529312 3.231709183 8.260073818 O -0.028484081 6.697449029 8.039214224 O 8.051754743 -0.130320836 8.225781644 O 6.058844101 3.817616332 8.230618129 O 3.886705450 6.902294086 7.980284767 O 1.910909959 1.117280091 4.757672837 O -0.004194776 4.491348467 4.795626713 O -1.935142427 7.846389802 4.788610091 O 5.846367748 1.122053313 4.615077267 O 3.880366054 4.491254094 4.747892833 O 1.926887127 7.841798686 4.811500749 O 9.750037570 1.160869507 4.786179704

O 7.810856137 4.496200746 4.776330234 O 5.795935012 7.887068185 4.755910378 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.855335806 1.047996499 7.093007328 Ce -0.013687328 4.507120728 7.202687472 Ce -1.970065672 7.781406637 7.156971636 Ce 5.869376692 1.138556545 6.910084370 * Reduced Ce4+ to Ce3+ Ce 3.925905450 4.589730994 7.150998221 * Reduced Ce4+ to Ce3+ Ce 1.952720416 7.824409749 7.169340106 Ce 9.776549405 1.155718309 7.139022389 Ce 7.855339979 4.569484845 7.145220852 Ce 5.809573615 7.882446119 7.106446390 Ce -0.002324360 2.255884406 3.952909579 Ce -1.940056774 5.617193883 3.952617340 Ce -3.906917786 8.980132671 3.941485212 Ce 3.867065406 2.255754066 3.951837829 Ce 1.942028432 5.611214869 3.975898953 Ce -0.005473431 8.958644195 3.949370358 Ce 7.808514831 2.269955753 3.936686743 Ce 5.831727772 5.624705202 3.956143671 Ce 3.880928578 8.994750523 3.958579576 Cu 5.657580510 2.555779255 9.494595619 Cu 3.218946599 2.566596553 9.361007791 Cu 4.467527485 0.498146530 9.451413122 Cu 6.883415951 0.470438431 9.518246860

Cu5 / CeO2(111) O -0.000014278 0.001087075 3.137151373 O -1.947254089 3.382702164 3.150967800 O -3.869251141 6.742276356 3.136563008 O 3.899604255 -0.006992294 3.140771028 O 1.934723687 3.363946593 3.162375975 O 0.009719088 6.757815604 3.152876616 O 7.784928628 0.011246982 3.173718490 O 5.874730618 3.368826704 3.155477174 O 3.902461746 6.771465441 3.156162431 O 0.048694104 2.249461754 6.359873736 O -1.946070351 5.689183299 6.410349943 O -3.797025586 8.968933459 6.350324293 O 3.742140579 2.272888589 6.392732971 O 1.980162391 5.675800036 6.396842647 O -0.009441111 8.923851460 6.396782997 O 7.807431987 2.287499974 6.320071133 O 5.924305421 5.643576983 6.339953369 O 3.908305682 9.021057040 6.250151267 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O -0.009013804 -0.071855046 7.890938469 O -2.061398320 3.318610748 8.013676593 O -3.835460352 6.804199002 8.038195109 O 3.880737843 -0.052819834 8.278309041 O 1.693625469 2.327496810 8.936448992 O -0.016771171 6.908304183 8.285811217 O 7.934162748 -0.040159969 7.984307483 O 6.084666782 3.404766241 8.252585488 O 4.047251023 7.143862601 8.119641318 O 1.931374284 1.080069282 4.713818516 O -0.007831858 4.524363451 4.738162579 O -1.927075645 7.866448518 4.782336949 O 5.798360206 1.123800895 4.774142661 O 3.922854228 4.506131525 4.613159260 O 1.940022890 7.884587334 4.768146203

O 9.753474240 1.163027778 4.779077729 O 7.827519586 4.523286520 4.785407617 O 5.894085805 7.876493827 4.769497305 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.835548136 1.007862861 7.043719538 Ce -0.105288436 4.493850086 7.153677824 * Reduced Ce4+ to Ce3+ Ce -1.934625378 7.874646676 7.243360683 Ce 5.875032367 1.109564645 7.203289091 * Reduced Ce4+ to Ce3+ Ce 3.974101434 4.556653597 6.893713553 * Reduced Ce4+ to Ce3+ Ce 2.003023816 7.995474349 7.080982285 Ce 9.720392021 1.140357863 7.126785676 Ce 7.861622328 4.506903058 7.169700819 Ce 5.935117755 7.902266719 7.116739638 Ce -0.002675969 2.264881613 3.940825122 Ce -1.927893210 5.632902891 3.962749983 Ce -3.866935907 8.975364852 3.927044545 Ce 3.894866067 2.222394855 3.948901758 Ce 1.929966711 5.637932458 3.948506975 Ce -0.005538110 8.999987275 3.970878261 Ce 7.784486646 2.257696237 3.971007715 Ce 5.886746134 5.633328656 3.922516830 Ce 3.910631486 9.008354010 3.937363454 Cu 1.234369551 6.085404300 9.375746849 Cu 2.345123179 3.949117928 9.468653638 Cu 3.609032558 5.956775735 9.453668170 Cu 4.768767831 3.721987033 9.504506127 Cu 3.420635900 1.499425480 9.294905241

Putative global minima PtmCun / CeO2(111) supported clusters Pt1Cu1 / CeO2(111) O -0.005630252 -0.008218431 3.171479570 O -1.936013524 3.360196202 3.148438980 O -3.900777183 6.746062629 3.174333569 O 3.878379225 0.000245582 3.144330142 O 1.945256611 3.385857490 3.180135509 O 0.000104129 6.739592775 3.151715042 O 7.786276431 -0.010327747 3.137881562 O 5.820018110 3.381501328 3.152403193 O 3.892386571 6.737354832 3.158454950 O 0.006982253 2.173147102 6.343240935 O -2.103417976 5.702907192 6.392039952 O -3.901147447 8.984394257 6.346003601 O 3.911723904 2.252069504 6.301831752 O 1.969649974 5.654205691 6.374044274 O 0.007687175 9.027559124 6.301984339 O 7.694854581 2.200015143 6.316387160 O 5.977408392 5.602215518 6.462459533 O 3.868430152 8.978328734 6.352926300 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O -0.052079220 -0.022334387 7.976069820 O -2.055847216 3.213319863 7.959770925 O -3.895331791 7.457305014 8.455636850 O 3.918764975 0.035471753 7.936674526 O 2.050661103 3.296340694 7.983664483 O -0.015258789 6.933951143 7.993939797 O 7.756758344 -0.020948260 7.965168444 O 5.613140567 3.227614397 8.187913232 O 3.904285656 6.746203879 7.985004811 O 1.952960635 1.119036413 4.780909331 O -0.038308077 4.517313035 4.793234454 O -1.931753068 7.883724950 4.766088067

O 5.822903999 1.113730162 4.738172659 O 3.914928103 4.533558667 4.818961903 O 1.939604281 7.867772160 4.778994625 O 9.702361593 1.116597750 4.785843420 O 7.800057655 4.446059475 4.703831348 O 5.811042716 7.845532688 4.814386042 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.936030967 1.137085074 7.135888326 Ce -0.016492828 4.503274939 7.229668352 * Reduced Ce4+ to Ce3+ Ce -1.877669705 7.957659873 7.136263526 Ce 5.801258756 1.077756463 7.133319654 Ce 3.826443912 4.493471593 7.148872972 Ce 1.927560220 7.877618446 7.162229008 Ce 9.719490579 1.074179554 7.151140003 Ce 7.871448668 4.334386973 7.001476869 Ce 5.768906517 7.914209771 7.188550539 Ce -0.008952042 2.253049788 3.987845249 Ce -1.937930075 5.627781227 3.963300940 Ce -3.897498466 8.990441862 3.973423975 Ce 3.889769747 2.248503024 3.958660473 Ce 1.933829846 5.625317225 3.985252116 Ce -0.006970354 8.991585873 3.939160665 Ce 7.772014904 2.216538002 3.922512896 Ce 5.837834387 5.625664971 3.982220909 Ce 3.887996494 8.977965768 3.961451137 Pt 8.222504072 5.848565202 9.395758453 Cu 6.238232359 4.454185263 9.416770242

Pt1Cu2 / CeO2(111) O 0.016414267 -0.005065382 3.167469312 O -1.939143662 3.368338587 3.165336137 O -3.881896272 6.742296271 3.147753004 O 3.895396375 -0.011752036 3.141909637 O 1.932117427 3.365965503 3.149031896 O -0.006946196 6.740061109 3.151887688 O 7.781851673 -0.010326031 3.166418687 O 5.844177596 3.359872029 3.163564116 O 3.890312625 6.755555130 3.158418980 O 0.023924432 2.199418290 6.282833242 O -1.910535159 5.636839401 6.383789355 O -3.883250557 9.015616680 6.307915152 O 3.957659662 2.342631052 6.419907459 O 1.955244758 5.597015431 6.377131643 O -0.016084160 8.975515086 6.360608535 O 7.780847794 2.163555368 6.316950918 O 5.742519638 5.590565771 6.366336460 O 3.927461323 8.977650146 6.313515357 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O 0.033406760 -0.012637748 7.955191676 O -1.799480065 3.274274709 7.968050500 O -3.897993922 6.910269260 7.984984974 O 3.862324697 -0.028050848 7.963509040 O 1.634127202 3.193803580 8.145051976 O 0.007537210 6.755585688 7.994165055 O 7.818246864 -0.117985523 7.949593028 O 6.626443076 2.560602016 8.718892628 O 3.879435813 7.031220775 8.137127179 O 2.009978385 1.132837553 4.791908276 O -0.000112918 4.502148874 4.792121434 O -1.945691463 7.858616598 4.788115017 O 5.807047842 1.096024687 4.785084219 O 3.867568943 4.497313963 4.658081278 O 1.927307584 7.850471330 4.793994667

O 9.738874659 1.110819374 4.772809003 O 7.787254129 4.504021320 4.771507443 O 5.873055564 7.842120421 4.783500148 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.936321944 1.068597876 7.136038025 Ce -0.063394357 4.478381935 7.157214295 Ce -1.954108532 7.866947177 7.167780890 Ce 5.889768359 1.017999926 7.217619771 Ce 3.849981088 4.541600564 6.895886905 Ce 1.890751078 7.892282752 7.147423909 Ce 9.751233499 1.100717486 7.123576480 Ce 7.865005602 4.472503756 7.244030014 * Reduced Ce4+ to Ce3+ Ce 5.904483956 7.911118658 7.140722139 Ce 0.006201444 2.243608863 3.958754425 Ce -1.956005273 5.605637966 3.978005221 Ce -3.878649760 8.984283087 3.951103051 Ce 3.910948958 2.218642899 3.949182856 Ce 1.910309481 5.630225945 3.925001903 Ce -0.003389470 8.990650063 3.960979582 Ce 7.783008690 2.239826037 3.985102360 Ce 5.873277910 5.621002919 3.950907132 Ce 3.898808853 8.981664738 3.966607787 Cu 3.885705896 5.875623530 9.561117700 Pt 5.252243637 3.859950488 9.213105126 Cu 2.837804958 3.659397842 9.471699591

Pt1Cu3 / CeO2(111) O -0.017371011 0.021916344 3.161895529 O -1.934078993 3.374848226 3.144617150 O -3.882294984 6.738635661 3.157869082 O 3.885972263 -0.012908903 3.157483429 O 1.937637253 3.372725175 3.153774429 O 0.006584811 6.728263667 3.153292732 O 7.794793067 -0.014132555 3.163415470 O 5.848781153 3.371187152 3.160768213 O 3.876017366 6.742726024 3.156239963 O 0.014786044 2.255243212 6.345739483 O -1.907961432 5.591667522 6.363865691 O -3.954334840 8.979935106 6.256157624 O 3.937063506 2.159537006 6.358768475 O 1.923712247 5.576409623 6.420464373 O 0.018654192 8.993119532 6.381450557 O 7.663953970 2.252710901 6.441080010 O 5.908918281 5.683526576 6.266443050 O 3.896798140 9.035231858 6.285284781 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O -0.021430363 0.001102580 7.945901762 O -1.882365761 3.352848855 7.977840997 O -3.819204105 6.818977444 7.934689876 O 3.553655237 -0.294465951 8.082129167 O 1.830284624 3.177241465 8.228011684 O 0.006334392 6.688824644 8.006792137 O 8.068930128 -0.183883128 8.151929863 O 6.177687724 4.479656190 8.640198471 O 3.909192601 6.912511337 7.965938847 O 1.938221604 1.140582997 4.763462396 O 0.007633994 4.491250594 4.801703255 O -1.924996511 7.844728828 4.784246878 O 5.848196207 1.097312894 4.670653995 O 3.892078065 4.483930436 4.752423047 O 1.933292865 7.827841439 4.808847021

O 9.699302021 1.188556385 4.816809930 O 7.827315999 4.477339446 4.779903936 O 5.811890182 7.879043013 4.738661522 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.855045909 1.050090396 7.100453753 Ce 0.002351008 4.485954082 7.198868965 Ce -1.954639530 7.781910830 7.142407179 Ce 5.804571742 1.054420805 6.912817187 Ce 3.971944246 4.621174239 7.187358707 * Reduced Ce4+ to Ce3+ Ce 1.980392222 7.802892663 7.165680678 Ce 9.766452843 1.142117024 7.151365259 Ce 7.855958701 4.598794889 7.211249877 Ce 5.831951250 7.887176611 7.105912741 Ce -0.004007944 2.260304302 3.957326621 Ce -1.941218961 5.606400039 3.960793542 Ce -3.901666533 8.984389123 3.942241688 Ce 3.873632284 2.261924937 3.950721534 Ce 1.957334118 5.602155620 3.979407632 Ce 0.003453399 8.943291754 3.932878090 Ce 7.797607759 2.276764252 3.957655686 Ce 5.842891319 5.621641330 3.956751636 Ce 3.884342504 8.990933720 3.959640296 Pt 5.750125686 2.630804193 9.237490601 Cu 3.268595817 2.608569065 9.298733830 Cu 4.523932436 0.476001772 9.474427242 Cu 6.952202934 0.483217750 9.473885644

Pt1Cu4 / CeO2(111) O 0.009127701 -0.005898861 3.149590105 O -1.938611959 3.377164646 3.159056386 O -3.887763198 6.742345661 3.158407319 O 3.895224568 -0.011245725 3.158451422 O 1.920912595 3.355244354 3.160835277 O 0.001764800 6.739619989 3.151423471 O 7.784185769 -0.009496699 3.150882915 O 5.867145328 3.351414487 3.149380077 O 3.892584418 6.767178802 3.161702068 O -0.014611295 2.221885807 6.294909096 O -1.967606953 5.603483802 6.368812104 O -3.920630256 8.980845027 6.404392379 O 3.884795311 2.179190794 6.282798971 O 1.991572776 5.640831121 6.337878025 O 0.021444162 8.999418952 6.377833360 O 7.847974782 2.200492134 6.272139835 O 5.841731784 5.679662284 6.338467885 O 3.889614589 8.988596825 6.315728491 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O -0.025196699 0.016849721 7.959870016 O -1.932136519 3.345244973 7.952019278 O -4.018152482 6.665196552 8.242758689 O 3.918885712 -0.027593498 8.102551988 O 1.535634049 3.287663316 8.111526894 O 0.113007486 6.680576087 8.026822451 O 7.802451790 0.009826884 7.963622593 O 6.278450279 3.231288686 8.053109265 O 3.861098576 7.199994569 8.274385549 O 1.932762458 1.088684148 4.776104133 O -0.005294863 4.519618320 4.791871648 O -1.938547638 7.855690496 4.775612275 O 5.862064590 1.099948688 4.772812171 O 3.908524668 4.479803451 4.592943365 O 1.926435167 7.869790544 4.787904488

O 9.746543866 1.104007906 4.757315222 O 7.793036894 4.493646030 4.764561532 O 5.851555515 7.888144280 4.774425313 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.864158707 1.090480928 7.096633396 Ce -0.047370643 4.528013690 7.127797479 Ce -1.916158211 7.825874980 7.244449441 * Reduced Ce4+ to Ce3+ Ce 5.942353277 1.064763409 7.100959591 Ce 3.916541948 4.441395110 6.878098710 * Reduced Ce4+ to Ce3+ Ce 1.907393401 7.889142799 7.147192809 Ce 9.740929484 1.118029288 7.112376759 Ce 7.899168239 4.433643906 7.071319514 Ce 5.823426052 7.953158118 7.105344055 Ce -0.001923650 2.240870372 3.940273995 Ce -1.938482793 5.630472570 3.945160550 Ce -3.881205322 8.977982105 3.961641637 Ce 3.898056796 2.210388178 3.922859848 Ce 1.934146089 5.630296210 3.939012356 Ce -0.001530672 8.975545777 3.960625602 Ce 7.796319126 2.232840133 3.924539724 Ce 5.857886911 5.632260874 3.934257436 Ce 3.891428365 8.992100936 3.941587583 Pt 3.848277970 1.539351013 9.323344319 Cu 3.930916440 5.809495037 9.462092219 Cu 5.117272500 3.677852070 9.440796742 Cu 6.345756988 5.799964675 9.271765217 Cu 2.694293625 3.746861856 9.468558629

Pt2Cu1 / CeO2(111) O -0.006785799 0.012163284 3.170453114 O -1.944397051 3.375567175 3.177734155 O -3.880649282 6.742463502 3.140096484 O 3.892369635 -0.016434666 3.134891118 O 1.921817750 3.366935605 3.138504529 O -0.004757396 6.741700840 3.144792801 O 7.790824248 -0.005184982 3.161850424 O 5.850987296 3.356890170 3.162575766 O 3.889217913 6.755600890 3.158410419 O 0.014987219 2.238268510 6.282439401 O -1.899613249 5.647517339 6.360571621 O -3.896780862 9.019822049 6.297621329 O 3.959236742 2.267859106 6.370975672 O 2.013606407 5.627248945 6.389675634 O -0.004519501 8.953439187 6.376244618 O 7.692413154 2.240504640 6.409575441 O 5.675214405 5.633035367 6.382663227 O 3.936625220 8.967967069 6.293581257 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O 0.020023353 0.040474418 7.930341873 O -1.801764679 3.319074485 7.972896783 O -3.872587333 6.925297261 7.971039944 O 3.840511973 -0.049027286 7.952310959 O 1.743888040 3.197374339 8.080559965 O 0.016430411 6.728471838 7.986355116 O 7.849218982 -0.098637263 7.898129898 O 6.378062811 2.011818811 9.194341065 O 3.951069976 7.471260499 8.443439027 O 1.986687519 1.133563126 4.767328864 O 0.020400936 4.524394931 4.800936597 O -1.947269953 7.868823841 4.780554543 O 5.826257380 1.078272618 4.764013168 O 3.866255372 4.466314708 4.630747165 O 1.928212388 7.853859054 4.790541551

O 9.694627364 1.142225487 4.811349401 O 7.773856042 4.529784883 4.773773638 O 5.876251205 7.849644342 4.764232212 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.928471673 1.062872876 7.107272143 Ce -0.044893472 4.500037376 7.162059033 Ce -1.946577144 7.873489581 7.162856515 Ce 5.860827726 0.992387721 7.240545970 Ce 3.830395118 4.437549481 6.865456315 Ce 1.918133595 7.905343242 7.172102403 Ce 9.737329328 1.130421245 7.136263011 Ce 7.875869645 4.559059916 7.215921103 * Reduced Ce4+ to Ce3+ Ce 5.897993447 7.948593630 7.159628031 Ce -0.002219369 2.258599901 3.957422226 Ce -1.951522204 5.619250637 3.967980970 Ce -3.890340094 8.982393967 3.943465637 Ce 3.910142369 2.198521180 3.923838684 Ce 1.917976642 5.636665953 3.923377499 Ce 0.005255834 8.987338167 3.962555852 Ce 7.763752260 2.249388659 4.005264436 Ce 5.862071202 5.633598382 3.953617421 Ce 3.893723170 8.989376058 3.967697049 Pt 3.984668632 5.737712235 9.340235534 Pt 5.466136483 3.687008467 9.175748377 Cu 2.979380670 3.436143869 9.462315955

Pt2Cu2 / CeO2(111) O -0.022025932 0.007389308 3.163188784 O -1.935218444 3.368564985 3.142066432 O -3.883221114 6.740572645 3.158895984 O 3.876033693 -0.025129866 3.152477646 O 1.936123985 3.371593251 3.154729908 O 0.008937624 6.727923019 3.151467305 O 7.798624195 -0.031387331 3.167094652 O 5.855238652 3.378415669 3.156353566 O 3.890932552 6.752926057 3.146745543 O 0.003327706 2.237293781 6.327270698 O -1.901182278 5.585978030 6.354226895 O -3.930925305 8.998782089 6.292583398 O 3.856136467 2.214502733 6.289423841 O 1.934189358 5.519791909 6.454369154 O 0.069408194 8.944744928 6.342142396 O 7.668057255 2.251697140 6.443767985 O 5.955842417 5.644933756 6.295504229 O 3.880968019 9.046845037 6.303837152 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O -0.009918174 -0.008848176 7.951032796 O -1.922390351 3.333894783 7.964614752 O -3.793837350 6.815624108 7.929587457 O 3.744730577 -0.268143499 7.991444716 O 1.407113592 3.135764558 8.460771490 O 0.012293984 6.704088202 8.003462626 O 8.069408527 -0.210079278 8.237397143 O 6.335206656 4.499893840 8.803923276 O 3.938605529 6.914657319 7.945225664 O 1.917885853 1.120788836 4.755293750 O 0.005718721 4.490089346 4.792605749 O -1.928062649 7.841683528 4.783210672 O 5.830803530 1.093111133 4.635178010 O 3.911815071 4.522855781 4.718797101 O 1.960283968 7.790880727 4.815673033 O 9.689117869 1.176696880 4.813649606

O 7.839863788 4.470234571 4.767896401 O 5.820980825 7.871107770 4.771021625 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.846102960 1.062104593 7.108071834 Ce -0.029383342 4.484843491 7.199680110 Ce -1.924121231 7.773200017 7.128042809 Ce 5.738116012 1.029937120 6.893984362 Ce 4.014741345 4.655543649 7.134265593 * Reduced Ce4+ to Ce3+ Ce 1.983191509 7.793005285 7.171012914 Ce 9.750536983 1.128592887 7.146578033 Ce 7.890432057 4.569757139 7.181044575 Ce 5.862304832 7.894300429 7.119887192 Ce -0.010094268 2.251996934 3.955799902 Ce -1.934323671 5.600441944 3.948219823 Ce -3.898557663 8.987935924 3.947878772 Ce 3.864908714 2.260191893 3.939856767 Ce 1.960640579 5.595890068 3.976328808 Ce 0.009116090 8.937139572 3.927125066 Ce 7.789703463 2.265187437 3.957240595 Ce 5.854544725 5.621064355 3.945386478 Ce 3.887048922 8.981790470 3.961558117 Pt 5.693067823 2.743657631 9.291251878 Pt 3.172626266 2.747479790 9.244997914 Cu 4.436102943 0.581216453 9.514719900 Cu 6.985284701 0.664430773 9.445555408

Pt2Cu3 / CeO2(111) O -0.000530900 0.023375167 3.186796601 O -1.938222815 3.359259801 3.155307718 O -3.876328541 6.734811639 3.149608946 O 3.879513697 -0.014412135 3.133311757 O 1.922888019 3.363135305 3.170385812 O -0.005483087 6.745785107 3.136116917 O 7.792079176 0.002432174 3.146680360 O 5.859243961 3.352017171 3.164354090 O 3.884035678 6.749399433 3.157482499 O 0.050891208 2.196270625 6.298094454 O -2.069712838 5.746871184 6.540185911 O -3.867368322 8.959890299 6.354171207 O 3.974333294 2.343960123 6.385993152 O 2.083443427 5.629248449 6.314205274 O -0.067287477 8.923078069 6.441400436 O 7.601391562 2.280856739 6.357809491 O 5.820226145 5.510696984 6.324606307 O 3.911229627 8.959703868 6.305468982 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O -0.011322314 0.129325052 8.017508048 O -2.022092819 3.234338759 7.917897139 O -3.564787767 7.427889662 8.746856407 O 3.795834107 0.034817721 7.973578072 O 1.865902335 3.208348391 8.234490025 O 0.319448842 6.710658292 8.311573583 O 7.871015389 -0.033139803 7.863225706 O 6.137015883 1.761372241 9.256991991 O 3.540155110 7.095790325 8.480119788 O 2.012779661 1.112990363 4.808555254 O -0.041851461 4.555058526 4.791592064 O -1.936679987 7.860783539 4.778023370 O 5.803862749 1.047396302 4.759366126 O 3.894896577 4.477238321 4.633904400 O 1.904889466 7.886612717 4.745172392 O 9.681390403 1.145769196 4.817990237

O 7.848188049 4.488933288 4.742801856 O 5.859610410 7.841989424 4.736376422 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.906268265 1.085233937 7.169083540 Ce -0.033490769 4.484793228 7.240654905 * Reduced Ce4+ to Ce3+ Ce -1.980227507 7.964835006 7.286776852 Ce 5.821718156 0.997790002 7.248904211 Ce 3.892700621 4.490077755 6.847481322 Ce 1.931327037 7.984996321 7.083946178 Ce 9.752267950 1.090603515 7.147823785 Ce 7.915171783 4.354617652 7.028267046 Ce 5.861535555 7.968581472 7.239505769 * Reduced Ce4+ to Ce3+ Ce -0.003593218 2.263200767 3.978704384 Ce -1.929349828 5.641235301 3.962514900 Ce -3.889564688 8.976497249 3.977818669 Ce 3.904251175 2.195895566 3.937355877 Ce 1.914348392 5.631639761 3.930146608 Ce -0.025154012 8.982894359 3.951448489 Ce 7.768511050 2.216721895 3.943586213 Ce 5.867503331 5.644152353 3.933591428 Ce 3.908101804 8.984833947 3.958529682 Pt 5.651089181 3.627744565 9.226807871 Pt 7.060160864 5.807241350 9.226528328 Cu 3.152516040 3.787878359 9.449658020 Cu 4.585782762 5.871444479 9.426228917 Cu 1.956049115 6.070086295 9.177410568

Pt3Cu1 / CeO2(111) O -0.004816847 -0.031248508 3.175450192 O -1.944027795 3.381557167 3.152429290 O -3.897265484 6.751936552 3.150351903 O 3.884669621 -0.013507367 3.162464760 O 1.917596642 3.358594762 3.135692564 O -0.014072441 6.757442391 3.141534794 O 7.783468134 -0.015820614 3.147610671 O 5.849336430 3.366599003 3.156403958 O 3.875334187 6.765602055 3.194075812 O -0.060758596 2.236702623 6.231077347 O -1.934985187 5.629091814 6.326954537 O -3.816348585 9.074886614 6.464417718 O 3.940593751 2.169570393 6.308852838 O 2.025497822 5.683813611 6.341497919 O -0.117294027 9.102391381 6.511767683 O 7.811608926 2.289093498 6.253591193 O 5.722169717 5.394102991 6.422539894 O 3.831134465 8.970920812 6.340537821 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O -0.065790453 0.164835093 7.990423856 O -1.870469742 3.389604229 7.910850783 O -3.835149141 6.604237213 7.997838459 O 3.687623283 -0.845361035 8.935224846 O 1.657546169 3.313112032 7.877866903 O 0.011395105 6.704287630 7.964697555 O 7.809312208 0.070672991 7.931487707 O 6.901803767 2.996360705 8.598171274 O 3.612731725 7.403433379 8.635377497 O 1.926135160 1.115548453 4.755706248 O 0.011999055 4.538108142 4.766557126 O -1.954821265 7.866260423 4.798401940 O 5.877788078 1.108361680 4.746732941 O 3.842915293 4.452243974 4.619990921

O 1.841968453 7.900933770 4.827848040 O 9.711551185 1.101940660 4.755204432 O 7.789861135 4.545203806 4.769446362 O 5.883361476 7.813323853 4.846285345 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.755276526 1.107440749 7.078268836 Ce -0.070445955 4.539644835 7.093705492 Ce -1.972338952 7.776085408 7.290826562 Ce 6.050520407 1.151404208 7.097525849 Ce 3.753257788 4.363987468 6.846223870 Ce 1.871167688 7.940427897 7.227204424 Ce 9.739530402 1.139136036 7.118114337 Ce 7.887147181 4.521015663 7.172457179 Ce 5.832356267 7.875836194 7.298204912 * Reduced Ce4+ to Ce3+ Ce -0.012690121 2.240452143 3.920094078 Ce -1.959505860 5.644497980 3.947828792 Ce -3.901706092 8.962853145 3.999860738 Ce 3.891880444 2.195225071 3.913101637 Ce 1.906038397 5.656114297 3.927592132 Ce -0.021394653 8.991732900 3.980589449 Ce 7.795104363 2.250428483 3.919365803 Ce 5.855885009 5.620668083 3.981013069 Ce 3.878411023 8.980147454 3.999224604 Pt 3.974064883 5.553515722 9.232301814 Pt 5.118035555 3.288744462 9.307901088 Pt 3.953957862 1.047861987 9.217533639 Cu 2.686286672 3.305155693 9.479968838

Pt3Cu2 / CeO2(111) O -0.017063289 -0.004646303 3.141909320 O -1.962414494 3.365688165 3.151489633 O -3.884347607 6.743534705 3.135012826 O 3.885356704 -0.000053914 3.152305096 O 1.938047312 3.366579609 3.155965333 O -0.004296748 6.758830708 3.154933549 O 7.781172757 0.004236583 3.176775927 O 5.854373039 3.365798330 3.150952067 O 3.919003217 6.766015202 3.164755422 O -0.019413829 2.277462972 6.349009425 O -1.989402746 5.655292163 6.368018053 O -3.787050291 9.078723835 6.471548483 O 3.721275743 2.332655662 6.352311552 O 2.047907881 5.591780061 6.320798227 O 0.053449091 8.937518961 6.336548102 O 7.790915426 2.247048525 6.323853569 O 5.828710531 5.610247943 6.273087383 O 3.871084751 8.943689972 6.280332934 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O -0.132890977 -0.053248692 7.854811392 O -2.089482400 3.324417143 8.012092948 O -3.996582313 6.697731753 8.025984122 O 4.665651883 -0.467037247 8.829369913 O 1.563845372 1.610651462 9.326363800 O 0.030931737 6.894611554 8.221431528 O 7.921943743 -0.065382950 8.000460922 O 5.982374108 3.474858139 8.070081187 O 4.085003040 6.889362589 8.060520679 O 1.887489874 1.099882799 4.706653681 O -0.021221870 4.515475018 4.704472060 O -1.968274789 7.876571135 4.767564629 O 5.787206735 1.130857227 4.779539883 O 3.924165367 4.495178342 4.644739363 O 1.947943290 7.847617783 4.769203353

O 9.738293016 1.129053800 4.790897632 O 7.797216577 4.508382631 4.778182527 O 5.925159085 7.895509789 4.809233809 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.708784632 1.093162582 7.007614684 Ce -0.165011154 4.492892165 7.093650012 * Reduced Ce4+ to Ce3+ Ce -1.946181750 7.843277046 7.279108872 Ce 5.927334925 1.069399635 7.186077485 * Reduced Ce4+ to Ce3+ Ce 3.973990218 4.538963134 6.858727010 Ce 2.008261709 7.946123702 7.104428960 Ce 9.673039298 1.121983709 7.146549193 Ce 7.818299114 4.513558761 7.163669329 Ce 5.905237721 7.879631828 7.147568602 Ce -0.034139044 2.261711136 3.911700042 Ce -1.949983646 5.640377160 3.957433692 Ce -3.867766104 8.980909125 3.947257395 Ce 3.884248487 2.220891128 3.939585644 Ce 1.924832074 5.633328844 3.936491941 Ce -0.009430309 8.987282542 3.983583647 Ce 7.769150729 2.246112748 3.967447349 Ce 5.885589805 5.634561012 3.912008737 Ce 3.899174226 8.995911700 3.950349264 Pt 1.191454969 5.766331123 9.336516107 Pt 2.218984990 3.488832522 9.264202073 Cu 3.634333403 5.663932672 9.439258245 Cu 4.687613558 3.266989924 9.377328870 Pt 3.443406272 0.946076429 9.231709969

Pt4Cu1 / CeO2(111) O -0.010389980 -0.018495428 3.156532486 O -1.952994700 3.363684326 3.148645582 O -3.893931586 6.741557028 3.131458573 O 3.892638042 -0.000623969 3.153055348 O 1.921495788 3.362415989 3.158461468 O -0.009360757 6.749288128 3.149873195 O 7.800266027 0.016803461 3.190905012 O 5.858050762 3.379861325 3.167189874 O 3.893025761 6.766642356 3.139328050 O 0.140112678 2.316290968 6.405135816 O -1.895232495 5.622473721 6.397111573 O -3.922977616 8.988597569 6.330650883 O 3.759591729 2.378329240 6.315869669 O 1.859448453 5.571540289 6.310871448 O 0.062759440 9.003260115 6.318151935 O 7.834871996 2.299430642 6.343861491 O 5.809443813 5.444933205 6.361765279 O 3.874975436 8.999853361 6.257286579 O 1.945943512 1.123508622 -0.007458684 0 0 0 O -0.000065583 4.493950135 -0.007364606 0 0 0 O -1.945992233 7.864467697 -0.007363162 0 0 0 O 5.837819924 1.123473163 -0.007269874 0 0 0 O 3.891879044 4.493954315 -0.007202975 0 0 0 O 1.945973422 7.864495846 -0.007283114 0 0 0 O 9.729789468 1.123537315 -0.007272123 0 0 0 O 7.783893843 4.493966618 -0.007215649 0 0 0 O 5.837915971 7.864501561 -0.007173318 0 0 0 O -0.000002077 2.246992724 1.603764045 0 0 0 O -1.945928584 5.617430747 1.603765689 0 0 0 O -3.891883464 8.988005991 1.603833932 0 0 0 O 3.891885581 2.246981810 1.603838953 0 0 0 O 1.945922669 5.617450509 1.603766532 0 0 0 O -0.000016518 8.987997589 1.603801497 0 0 0 O 7.783841637 2.247030278 1.603822149 0 0 0 O 5.837892778 5.617459095 1.603804665 0 0 0 O 3.891925509 8.988016142 1.603780083 0 0 0 O -0.094573384 -0.084957630 7.872656172 O -1.848928364 3.366634475 7.947145046 O -4.002519282 6.705945757 7.972321558 O 3.924178934 -0.141812305 8.201261380 O 1.547158368 1.724264339 9.267601610 O -0.006962043 7.055380473 8.176812635 O 7.956239354 -0.043922167 8.019081668 O 6.837473592 3.314862187 8.793493548 O 3.954790168 6.935798739 7.941367834 O 1.930129673 1.080150892 4.730758764 O -0.052356899 4.486638224 4.739287329 O -1.963693149 7.861711721 4.745485272 O 5.816111660 1.159879292 4.768160208 O 3.864451076 4.541686476 4.617162913 O 1.944470112 7.844839076 4.762295474 O 9.789593175 1.165213704 4.824302268

O 7.822442491 4.541479728 4.781292095 O 5.855922719 7.800843413 4.794371617 Ce 0.000034891 0.000035348 0.790754446 0 0 0 Ce -1.945940043 3.370523402 0.790768980 0 0 0 Ce -3.891876564 6.741033272 0.790804396 0 0 0 Ce 3.891878580 0.000053748 0.790779682 0 0 0 Ce 1.945934797 3.370452531 0.790735408 0 0 0 Ce -0.000011749 6.740956919 0.790739214 0 0 0 Ce 7.783804261 0.000034103 0.790779091 0 0 0 Ce 5.837875435 3.370504547 0.790810310 0 0 0 Ce 3.891908164 6.740915165 0.790819701 0 0 0 Ce 1.863644682 0.990833190 7.088556605 Ce -0.134846430 4.467966725 7.057578786 Ce -2.005318676 7.878973599 7.185824504 * Reduced Ce4+ to Ce3+ Ce 5.947709770 1.099269249 7.227743487 * Reduced Ce4+ to Ce3+ Ce 3.815930491 4.583799125 6.830412815 Ce 1.958129637 7.994970115 7.105285359 Ce 9.745460496 1.107835470 7.157470136 Ce 7.877892250 4.524146578 7.217284812 Ce 5.862407344 7.854941649 7.116013392 Ce 0.002452845 2.241765958 3.938143282 Ce -1.960814660 5.631086736 3.938439487 Ce -3.885167059 8.971766947 3.936059066 Ce 3.891511386 2.221678825 3.948984158 Ce 1.897642863 5.647206652 3.902087743 Ce -0.004562970 9.014829682 3.981633830 Ce 7.789469164 2.265112375 3.987647032 Ce 5.872611300 5.612552230 3.925217509 Ce 3.892128971 8.985498326 3.946847930 Pt 1.034259877 5.872888407 9.334504528 Pt 2.190389144 3.660711224 9.231379848 Cu 3.539910373 5.821457506 9.422874379 Pt 4.986229575 3.723223345 9.210364727 Pt 3.649835898 1.565801005 9.286312237

Electronic Structure Analysis Projected Density of States (PDOS) pristine CeO2(111) surface

Figure S3. Projected density of states (PDOS) in arbitrary units, calculated for the pristine surface CeO2(111). The location of the O(2p), Ce4+(5d), as well as the Ce4+(4f) and Ce3+(4f) orbitals is shown.

Projected Density of States (PDOS) global minima CuN /CeO2(111) clusters

Figure S4. Spin polarized projected density of states (PDOS) in arbitrary units, calculated for Cu1/CeO2(111). The location of the Cu(4s,3d), O(2p), Ce4+(5d), as well as the Ce4+(4f) and Ce3+(4f) orbitals is shown.

Projected Density of States (PDOS) global minima PtN /CeO2(111) clusters

Figure S9. Spin polarized projected density of states (PDOS) in arbitrary units, calculated for Pt1/CeO2(111). The location of the Pt(6s,5d), O(2p), Ce4+(5d), as well as the Ce4+(4f) and Ce3+(4f) orbitals is shown.

Projected Density of States (PDOS) global minima PtmCun /CeO2(111) clusters

Figure S14. Spin polarized projected density of states (PDOS) in arbitrary units, calculated for Pt1Cu1/CeO2(111). The location of the Pt(6s,5d), Cu(4s,3d), O(2p), Ce4+(5d), as well as the Ce4+(4f) and Ce3+(4f) orbitals is shown.

ceo2 (111) electronic reducibility tuned by ultra-small ... · 1 ceo2 (111) electronic reducibility...

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