Supporting Information File for. Design of van der Waals Two-Dimensional Heterostructures from

Supporting Information File for Design of van der Waals Two-Dimensional Heterostructures from Facially Polarized Janus all-cis 1,2,3,4,5,6-hexafluorocyclohexane (C 6 H 6 F 6 ) Saied Md Pratik, 1 A. Nijamudheen, 2 Ayan Datta 1 * 1 Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur- 700032, West Bengal (India), 2 Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, NY 14260-3000 *Email: spad@iacs.res.in Contents 1. Figure S1: HOMO and LUMO plots for 1-X, 1-Y and X-1-Y complexes. 2. Details of NCIPLOT calculations and Figure S2: Reduced density gradient (s) vs sign(λ2)ρ plot using NCIPLOT program for 1-X, 1-Y and X-1-Y complexes. 3. Figure S3: Band structure of Hydroflourinated graphene (HFG) monolayer using GGA-PBE functional. 4. Figure S4: Calculated total density of states (TDOS) and partial density of states (PDOS) for HFG-graphane bilayer using GGA-PBE functional. 5. Figure S5: Band structure of HFG-graphene and graphene-hfg-graphane heterostructures using GGA-PBE functional. S1

6. Cartesian Coordinates for the optimized structures, their zero point energy corrected total energies in Hartree and low frequencies calculated at M06/6-31+G(d,p) level of theory in the gas phase. Harmonic Frequencies calculated at 298K. 7. Complete Reference for Gaussian 09 and Amsterdam Density Functional Theory (ADF) software package. 1. Figure S1: HOMO and LUMO plots for 1-X, 1-Y and X-1-Y complexes. S2

Figure S1: The HOMO and HUMO plot for 1-benzene, 1-pyrene, 1-cyclohexane, 1- perhydropyrene, benzene-1-cyclohexane and pyrene-1-perhydropyrene. 2. Details of NCIPLOT calculations: The nature of dispersion interactions between the 1-X, 1-Y and X-1-Y are demonstrated by NCIPLOT analysis. This provides a simple distinction between attractive and repulsive domains of Non-Covalent Interactions. The 2D-plot produce by NCIPLOT, contains the reduce electron density gradient (s) and electron density values (ρ). The s and ρ are connected by the following relations 1 = 2(3 ) The stabilization or destabilization interactions arise in the complexes can be determined from the sign of 2 ρ at critical bonding points. The negative sign of 2 ρ indicates net gradient flux of electron density is localized (stabilizing interaction) whereas the positive sign indicates the net gradient flux of electron density is diminishing (destabilizing interaction). To obtained the NCIPLOT from DFT wave functions, the reduced density gradient (RDG) s(r) have to be plotted onto the sign(λ 2 )ρ(r). Herein, λ 2 (second eigenvalue of the electron density Hessian matrix) is represented as 2 ρ =λ 1 + λ 2 + λ 3 (where, λ 1 < λ 2 < λ 3 ). λ 3 varies along inter-nuclear distance whereas, λ 1 and λ 2 vary along the normal to the λ 3 eigenvector. Depending on the nature of interactions λ 2 can be negative or positive. The negative of λ 2 indicates stabilizing while the positive indicates destabilizing interactions. Hence, by analyzing the sign of λ 2 one can distinguish the attractive (stabilizing) or repulsive (destabilizing) interactions. These plots are S3

obtained from M06 functional and reduced gradient on cuboids grids, with a 0.1 au step size for each complex. Figure S2: Reduced density gradient (s) vs sign(λ2)ρ plot using NCIPLOT program for 1-X, 1-Y and X-1-Y complexes. Figure S2: Reduced density gradient (s) vs sign(λ2)ρ plot using NCIPLOT program for (a) 1- benzene, (b) 1-pyrene, (c) 1-coronene, (d) 1-cyclohexane, (e) 1-perhydropyrene, (f) 1- perhydrocoronene, (g) benzene-1-cyclohexane, (h) pyrene-1-perhydropyrene and (i) coronene-1- perhydrocoronene. S4

3. Figure S3: Band structure of Hydroflourinated graphene (HFG) monolayer. Figure S3: Calculated band structure of Hydroflourinated graphene (HFG) monolayer using GGA-PBE functional. 4. Figure S4: Total density of states (TDOS) and partial density of states (PDOS) for HFGgraphane bilayer. S5

Figure S4: Calculated total density of states (TDOS) HFG-graphane bilayer (black line) and partial density of states (PDOS) of graphane (red line) and HFG (green line), respectively. and partial density of states. 5. Figure S5: Band structure of HFG-graphene and graphene-hfg-graphane heterostructures using GGA-PBE functional. (a) (b) Figure S5: Calculated band structure of (a) HFG-graphene (b) graphene-hfg-graphane heterostructures. The energy is scaled with respect to Fermi level. 6. Cartesian Coordinates for the optimized structures, their zero point energy corrected total energies in Hartree and low frequencies calculated at M06/6-31+G(d,p) level of theory in the gas phase. Harmonic Frequencies calculated at 298K. (a) 1-benzene Center Atomic Coordinates (Angstroms) Number Number X Y Z 1 6 1.367550 0.273015 3.091259 2 6 0.919528-1.048181 3.091616 3 6-0.447337-1.320840 3.091259 S6

4 6-1.367515-0.272244 3.091616 5 6-0.920213 1.047825 3.091259 6 6 0.447987 1.320425 3.091616 7 6 1.236312-0.713478-0.672809 8 6 1.275294 0.736606-1.127613 9 6-0.000266 1.427417-0.672809 10 6-1.275567 0.736134-1.127613 11 6-1.236046-0.713939-0.672809 12 6 0.000273-1.472740-1.127613 13 9 0.000000 2.732685-1.096993 14 9 1.418238 0.818668-2.486426 15 9-1.418107 0.818896-2.486426 16 9-2.366575-1.366343-1.096993 17 9-0.000131-1.637564-2.486426 18 1 0.000000 1.427244 0.431363 19 1 2.142809 1.237530-0.672993 20 1-2.143136 1.236962-0.672993 21 1-1.236029-0.713622 0.431363 22 1 1.236029-0.713622 0.431363 23 1 0.000328-2.474491-0.672993 24 1-0.796956-2.350968 3.098753 25 1 1.637389-1.865569 3.098933 26 1-2.434325-0.485235 3.098933 27 1-1.637520 1.865668 3.098753 28 1 0.796936 2.350805 3.098933 29 1 2.434476 0.485300 3.098753 30 9 2.366575-1.366343-1.096993 ENERGY=-1063.059484 Hartree Frequencies 7.4327 7.4327 51.8563 58.3454 58.3454 72.1806 129.6965 129.6965 183.0086 (b) 1-pyrene Center Atomic Coordinates (Angstroms) Number Number X Y Z 1 6 1.998347 3.494303 0.270978 2 6 2.137819 2.872058-0.965105 3 6 2.182129 1.476174-1.062044 4 6 2.083294 0.696836 0.124916 5 6 1.949857 1.340594 1.387152 6 6 1.908203 2.739817 1.435902 7 6 2.286138 0.800070-2.323031 S7

8 6 2.074607-0.724328 0.045406 9 6 2.164799-1.367630-1.221127 10 6 2.277795-0.556469-2.398941 11 6 2.103351-2.764989-1.280424 12 1 2.159671-3.255609-2.250482 13 6 1.955574-3.519438-0.121309 14 6 1.873993-2.898491 1.120596 15 6 1.932640-1.503158 1.228102 16 1 2.363171 1.404052-3.225649 17 1 1.956285 4.579075 0.326342 18 1 2.200741 3.467076-1.874453 19 1 1.800408 3.231703 2.401331 20 1 2.347760-1.056986-3.363314 21 1 1.900637-4.603053-0.187196 22 1 1.760216-3.493579 2.025325 23 6 1.830537-0.827329 2.489592 24 6 1.838584 0.529610 2.565444 25 1 1.734860-1.430200 3.391291 26 1 1.749195 1.029310 3.528767 27 9-3.500890-1.433701 0.446992 28 9-2.416147-0.175665 2.643052 29 9-3.484687 1.388105 0.642260 30 9-1.766952 2.465190-1.232684 31 9-3.115056 0.144872-1.875217 32 9-1.790634-2.258213-1.563019 33 6-2.143231-1.311786 0.582105 34 6-1.791686-0.094047 1.422778 35 6-2.128678 1.232969 0.759880 36 6-1.456417 1.285802-0.602171 37 6-1.795946 0.111288-1.506180 38 6-1.470119-1.181078-0.774341 39 1-1.777871-2.220259 1.083348 40 1-0.701791-0.112104 1.600803 41 1-1.754105 2.058466 1.383051 42 1-0.366120 1.269065-0.433052 43 1-1.193315 0.171920-2.424465 44 1-0.379981-1.198831-0.603169 ENERGY=-1446.3185059 Hartree Frequencies 7.4942 22.0004 26.4176 44.7109 46.3337 63.5473 109.4402 126.4399 131.4600 S8

(c) 1-coronene Center Atomic Coordinates (Angstroms) Number Number X Y Z 1 6-1.683471-1.394352-0.256005 2 6-1.275299-0.894156-1.525480 3 6-1.196123 0.510032-1.745193 4 6-1.525022 1.414815-0.695747 5 6-1.927244 0.914789 0.574928 6 6-2.006457-0.490037 0.794785 7 6 1.974944-1.350401 0.076928 8 6 2.014566-1.144925 1.582671 9 6 1.464562 0.234903 1.908413 10 6 2.160199 1.368580 1.171524 11 6 2.114958 1.089707-0.322241 12 6 2.680780-0.264368-0.719416 13 6-0.738982 1.006697-2.989576 14 6-0.896528-1.793117-2.551101 15 6-1.715485-2.790119-0.022779 16 6-2.358794-0.987186 2.072450 17 6-2.201038 1.813046 1.634011 18 6-1.399877 2.810026-0.899549 19 6-0.634074 2.411440-3.170618 20 6-0.954169 3.281106-2.163277 21 6-0.379022 0.082414-4.006499 22 6-0.454979-1.267950-3.795005 23 6-0.949945-3.188824-2.293911 24 6-1.346478-3.669695-1.075198 25 6-2.095073-3.262455 1.262215 26 6-2.404829-2.392789 2.272914 27 6-2.636257-0.063274 3.114894 28 6-2.560143 1.287062 2.903465 29 6-2.089818 3.209050 1.395654 30 6-1.704054 3.690019 0.173415 31 1-2.123647-4.337228 1.433414 32 1-1.371063-4.742036-0.889521 33 1-0.655896-3.875310-3.085917 34 1-0.166555-1.964638-4.580332 35 1-0.029493 0.470579-4.961720 S9

36 1-0.278893 2.787269-4.128526 37 1-0.856697 4.354886-2.313288 38 1-1.612346 4.762211 0.008199 39 1-2.308117 3.894867 2.212528 40 1-2.763994 1.982489 3.715787 41 1-2.901266-0.451275 4.096869 42 1-2.682467-2.768784 3.256203 43 9 1.524582 0.453174 3.262549 44 9 3.291043-1.285167 2.060245 45 9 3.454022 1.506351 1.601276 46 9 2.770385 2.085873-1.002745 47 9 4.033403-0.306506-0.505128 48 1 0.401535 0.246935 1.611497 49 1 1.391041-1.909724 2.070348 50 1 1.637631 2.314163 1.381713 51 1 1.055945 1.109432-0.630348 52 1 0.914707-1.348461-0.227783 53 1 2.506426-0.430131-1.793775 54 9 2.502350-2.577668-0.240130 ENERGY=-1752.2305275 Hartree Frequencies 6.0148 14.3235 22.2167 41.1134 63.8901 69.2302 89.9431 91.7905 139.0582 (d) 1-Cyclohexane Center Atomic Coordinates (Angstroms) Number Number X Y Z 1 6-3.247461 0.096850-1.448140 2 6-2.779836 1.307763-0.646767 3 6-3.237268 1.219213 0.806072 4 6-2.770818-0.082106 1.451772 5 6-3.235863-1.294901 0.651527 6 6-2.782708-1.205188-0.802765 7 1-2.883151 0.160318-2.483004 8 1-1.679812 1.352320-0.672373 9 1-2.865730 2.081959 1.376395 10 1-1.670630-0.084148 1.497776 11 1-2.861244-2.220524 1.110345 12 1-1.683027-1.249718-0.839722 13 9 0.370856 0.109619-1.624712 14 9 1.784068 2.437509-1.219662 S10

15 9 0.388891 1.371605 0.899689 16 9 1.758200-0.173614 2.724202 17 9 0.358297-1.453280 0.727276 18 9 1.728063-2.282841-1.508714 19 6 1.730340 0.084182-1.471580 20 6 2.199987 1.268689-0.640009 21 6 1.746384 1.223212 0.812067 22 6 2.185950-0.098466 1.425551 23 6 1.718568-1.325108 0.655980 24 6 2.171566-1.203823-0.791744 25 1 2.175471 0.141154-2.475032 26 1 3.304134 1.260865-0.643802 27 1 2.204454 2.054789 1.366051 28 1 3.290150-0.110601 1.429808 29 1 2.157868-2.228157 1.102994 30 1 3.275618-1.221517-0.797671 31 1-4.337594-1.350718 0.684690 32 1-3.152160-2.068714-1.373135 33 1-3.129736-0.146672 2.488359 34 1-4.349813 0.101847-1.502095 35 1-4.339221 1.268143 0.843479 36 1-3.143987 2.236474-1.107565 ENERGY=-1066.6787851 Hartree Frequencies 31.1313 34.9133 60.9074 65.9742 87.6381 99.1116 133.9145 139.9578 184.8524 (e) 1-perhydropyrene Center Atomic Coordinates (Angstroms) Number Number X Y Z 1 6-2.585509-3.509318 0.017049 2 6-2.100640-2.803375-1.243155 3 1-1.002017-2.892612-1.313872 4 1-3.687954-3.500913 0.034297 5 6-2.060179-2.812229 1.265821 6 1-0.960662-2.907387 1.301884 7 6-2.463463-1.322274-1.238732 8 6-2.318909 0.866640-2.484774 9 6-1.994851-0.620147-2.508058 10 1-0.904517-0.753764-2.603513 11 1-3.569176-1.241004-1.194597 S11

12 1-3.414784 1.006244-2.482795 13 6-2.414741-1.328931 1.284454 14 6-2.226731 0.861809 0.026397 15 6-2.055203 3.039687-1.224344 16 6-2.189180 0.851869 2.537284 17 6-1.975395 3.030086 1.282243 18 6-1.911630-0.635269 0.014357 19 6-1.738135 1.548887-1.252031 20 6-1.885053-0.639230 2.536621 21 6-1.664800 1.537270 1.280649 22 6-1.483630 3.717413 0.014673 23 1-0.806718-0.738110 0.000000 24 1-0.637461 1.433451-1.285544 25 1-0.793955-0.788183 2.584270 26 1-0.563885 1.411680 1.253758 27 1-0.383550 3.664683-0.021001 28 1-3.520713-1.240598 1.287809 29 1-3.333870 0.973708 0.057983 30 1-3.152520 3.167832-1.238871 31 1-3.281746 1.006102 2.591723 32 1-3.069105 3.161643 1.367693 33 1-1.747014 4.783889 0.027513 34 1-1.675501 3.517731-2.139797 35 1-2.282864-4.565291 0.000000 36 1-2.512039-3.286642-2.142251 37 1-2.447260-1.103867-3.387007 38 1-1.945726 1.359709-3.394884 39 9 1.755011 1.642959 0.048368 40 9 3.017147 1.233573-2.362726 41 9 1.349548-0.744551-1.418146 42 9 2.466579-2.878921-0.093392 43 9 1.418123-0.809276 1.390496 44 9 3.144867 1.105062 2.362976 45 6 3.074170 1.280781 0.000000 46 6 3.374992 0.496505-1.265710 47 6 2.709212-0.870596-1.322300 48 6 3.086790-1.658155-0.076459 49 6 2.771183-0.937069 1.225494 50 6 3.440585 0.428735 1.209748 51 1 3.668846 2.205195 0.012532 52 1 4.466712 0.335292-1.305099 53 1 3.053041-1.409495-2.216485 54 1 4.177094-1.829656-0.107110 55 1 3.152146-1.523975 2.073169 56 1 4.532098 0.264219 1.181918 57 1-1.764052 1.333676 3.430502 S12

58 1-2.305609-1.122322 3.431597 59 1-1.536719 3.500105 2.175212 60 1-2.445285-3.299490 2.174350 ENERGY=-1455.9493937 Hartree Frequencies 22.9473 36.8923 46.1046 57.0496 69.5943 77.7693 106.8272 128.8083 137.0939 (f) 1-perhydrocoronene Center Atomic Coordinates (Angstroms) Number Number X Y Z 1 6-1.141463 3.745080 1.473036 2 6-0.008130 3.123735 2.275479 3 1 0.912322 3.112969 1.665475 4 1-2.036556 3.837242 2.113485 5 6-2.654584 3.510863-0.531640 6 6-1.499883 2.902309 0.254880 7 6-3.022116 2.663743-1.740582 8 1-0.612401 2.865522-0.408257 9 1-2.177643 2.657036-2.452342 10 1-3.529710 3.596117 0.136519 11 6-0.330626 1.692234 2.687120 12 6 0.498323-0.373368 3.873613 13 6 0.798474 1.070648 3.500565 14 1 1.725020 1.107339 2.903895 15 1-1.237493 1.715711 3.325867 16 1-0.373207-0.407440 4.551574 17 6-1.814874 1.458260 0.657885 18 6-0.963489-0.609004 1.843140 19 6-0.100595-2.667673 3.008203 20 6-3.335076 1.223878-1.350664 21 6-2.459646-0.844014-0.181677 22 6-1.584077-2.909005 0.987229 23 6-3.953291-1.073340-2.192578 24 6-3.060389-3.135156-1.041131 25 6-0.666895 0.840918 1.458769 26 6 0.191965-1.217839 2.642899 27 6-2.174780 0.609395-0.562691 28 6-1.302439-1.451438 0.612537 29 6-0.423838-3.501481 1.777404 30 6-3.677759 0.374625-2.569207 S13

31 6-2.791288-1.683878-1.418923 32 6-1.904729-3.733594-0.253346 33 1 0.228401 0.831368 0.803833 34 1 1.084986-1.203495 1.988003 35 1-1.290626 0.603729-1.231808 36 1-0.410501-1.446888-0.047356 37 1 0.462791-3.543716 1.121132 38 1-2.827504 0.412705-3.272814 39 1-1.895630-1.662872-2.072611 40 1-1.004140-3.769447-0.892038 41 1-2.707659 1.486287 1.321017 42 1-1.858391-0.606989 2.504373 43 1-0.957814-2.692177 3.704513 44 1-4.218764 1.234264-0.680712 45 1-3.357482-0.851266 0.474859 46 1-2.480005-2.913292 1.641314 47 1-4.860325-1.124541-1.564759 48 1-3.980448-3.177039-0.431721 49 1-0.655713-4.539894 2.058206 50 1 0.754064-3.093479 3.554788 51 1-2.124126-4.772805 0.034060 52 1-3.263158-3.724853-1.947645 53 1-4.163625-1.675789-3.088923 54 1-4.537536 0.811491-3.098913 55 1-3.877200 3.099911-2.278512 56 1-2.398972 4.536411-0.837628 57 1-0.882170 4.766280 1.155797 58 1 0.214980 3.728682 3.167199 59 1 0.982302 1.676231 4.400875 60 1 1.339751-0.814395 4.428708 61 9 2.043230-1.675844-0.556456 62 9 4.543127-1.366453 0.547496 63 9 2.817769 0.779145 0.630468 64 9 3.068144 2.736257-1.282403 65 9 1.161142 0.786296-1.635545 66 9 1.752382-1.347540-3.270219 67 6 3.136501-1.469399-1.353786 68 6 4.214849-0.700969-0.603294 69 6 3.840630 0.737591-0.278382 70 6 3.443188 1.449210-1.562637 71 6 2.336792 0.747004-2.335765 72 6 2.753086-0.691449-2.604408 73 1 3.523485-2.457337-1.640906 74 1 5.111046-0.672753-1.247891 75 1 4.702814 1.247789 0.173864 76 1 4.334030 1.487704-2.213766 S14

77 1 2.168361 1.265051-3.290453 78 1 3.639256-0.663435-3.262672 ENERGY=-1766.6507584 Hartree Frequencies 7.6626 19.1122 33.6382 50.4397 54.5140 73.3066 78.5453 85.2429 123.5886 (g) benzene-1-cyclohexane Center Atomic Coordinates (Angstroms) Number Number X Y Z 1 6-4.707045-1.312947 0.934463 2 6-4.450103-1.735083-0.368890 3 6-4.381190-0.802043-1.403654 4 6-4.567388 0.553384-1.133452 5 6-4.822268 0.975413 0.171627 6 6-4.892642 0.042107 1.204834 7 1-4.756367-2.039029 1.742140 8 1-4.310851-2.792965-0.580566 9 1-4.196541-1.133709-2.423695 10 1-4.528777 1.280382-1.942632 11 1-4.974299 2.032107 0.381477 12 1-5.089549 0.370111 2.222661 13 9 0.752336-1.249455 0.622405 14 9 0.347149-1.412422-2.098106 15 9 1.363060 0.932258-1.075164 16 9-0.371296 3.020827-0.610767 17 9 0.326252 1.403906 1.514830 18 9-1.427384-0.624680 2.220103 19 6-0.505692-1.122891 0.094866 20 6-0.443843-0.595838-1.330667 21 6 0.044672 0.841139-1.436690 22 6-0.818561 1.725853-0.549989 23 6-0.888859 1.266262 0.898451 24 6-1.356031-0.177627 0.924013 25 1-0.967749-2.121180 0.096586 26 1-1.469449-0.631265-1.738283 27 1-0.032482 1.179659-2.479705 28 1-1.846712 1.700038-0.952049 29 1-1.611334 1.890044 1.445467 30 1-2.374135-0.199201 0.502007 31 6 4.037185-1.439709 1.051109 32 6 3.899849 0.012890 1.496978 S15

33 6 5.014226 0.874460 0.910370 34 6 5.049031 0.768504-0.611567 35 6 5.180453-0.684454-1.059457 36 6 4.066875-1.545753-0.470580 37 1 4.892434 1.921759 1.218635 38 1 2.924693 0.399704 1.160299 39 1 3.900566 0.079402 2.593521 40 1 4.972919-1.857900 1.460712 41 1 3.216192-2.043275 1.459893 42 1 4.115139 1.186401-1.020219 43 1 5.870874 1.372493-1.020685 44 1 5.178321-0.749650-2.156279 45 1 6.155937-1.077159-0.724871 46 1 3.096546-1.208686-0.870258 47 1 4.187672-2.592893-0.781095 48 1 5.983885 0.538903 1.316644 ENERGY=-1298.7629943 Hartree Frequencies 10.0824 24.8256 29.5354 33.8479 59.2381 62.2928 64.9537 69.6355 75.9808 (h) pyrene-1-perhydropyrene Center Atomic Coordinates (Angstroms) Number Number X Y Z 1 6 4.722408 3.515244-0.166174 2 6 4.268671 2.736393-1.394780 3 1 3.169571 2.797953-1.480998 4 1 5.824552 3.540688-0.140407 5 6 4.208334 2.863095 1.111401 6 1 3.105375 2.919772 1.134723 7 6 4.663628 1.265248-1.316223 8 6 4.558046-0.985558-2.453825 9 6 4.208556 0.492570-2.549275 10 1 3.116136 0.601555-2.649938 11 1 5.770920 1.209746-1.269188 12 1 5.656193-1.107020-2.447891 13 6 4.613315 1.395570 1.202493 14 6 4.473527-0.859349 0.053149 15 6 4.331043-3.098935-1.089697 16 6 4.454064-0.729375 2.559423 S16

17 6 4.269055-2.969607 1.413136 18 6 4.126001 0.628241-0.030776 19 6 3.991298-1.616152-1.187466 20 6 4.114602 0.752498 2.491680 21 6 3.932527-1.484342 1.342127 22 6 3.777000-3.724098 0.184450 23 1 3.019449 0.707644-0.056504 24 1 2.889087-1.518386-1.220586 25 1 3.021325 0.875496 2.546083 26 1 2.829725-1.380339 1.317111 27 1 2.676105-3.686229 0.155152 28 1 5.721791 1.343931 1.202285 29 1 5.583089-0.946904 0.083189 30 1 5.430178-3.211701-1.105317 31 1 5.550460-0.856987 2.608841 32 1 5.365593-3.079468 1.494685 33 1 4.054682-4.785336 0.246302 34 1 3.952751-3.626099-1.978445 35 1 4.388683 4.560161-0.227521 36 1 4.679271 3.184698-2.312342 37 1 4.652489 0.940497-3.451372 38 1 4.191083-1.528594-3.337728 39 9 0.419464-1.789373-0.021747 40 9-0.928299-1.253925-2.383741 41 9 0.865437 0.627607-1.434551 42 9-0.110328 2.756480-0.005523 43 9 0.876123 0.621279 1.396190 44 9-0.897450-1.269548 2.352230 45 6-0.888337-1.375206-0.015955 46 6-1.202365-0.538540-1.244210 47 6-0.487288 0.800612-1.286011 48 6-0.794044 1.565782-0.007834 49 6-0.478657 0.793125 1.263030 50 6-1.191234-0.547940 1.221709 51 1-1.521527-2.275148-0.017826 52 1-2.284260-0.331886-1.229153 53 1-0.843805 1.377532-2.152422 54 1-1.873880 1.792787-0.005309 55 1-0.826765 1.365010 2.136066 56 1-2.274281-0.344952 1.223339 57 1 4.048479-1.177527 3.478964 58 1 4.533900 1.287735 3.357256 59 1 3.845228-3.402800 2.331601 60 1 4.569116 3.407048 1.997645 61 6-4.927806-3.387896-0.219259 62 6-4.859634-2.627005-1.381750 S17

63 6-4.746142-1.232923-1.318097 64 6-4.693946-0.600955-0.044102 65 6-4.766578-1.385629 1.140852 66 6-4.883283-2.776602 1.029335 67 6-4.657826-0.418051-2.495769 68 6-4.538435 0.811748 0.044941 69 6-4.437762 1.593690-1.140374 70 6-4.510429 0.930400-2.411119 71 6-4.251814 2.977753-1.028804 72 1-4.171260 3.575053-1.935577 73 6-4.166960 3.585091 0.220155 74 6-4.268415 2.827602 1.382738 75 6-4.455856 1.440611 1.319318 76 1-4.698664-0.909513-3.466259 77 1-5.013276-4.469445-0.287264 78 1-4.890455-3.109938-2.356854 79 1-4.933332-3.376323 1.936468 80 1-4.438010 1.535871-3.313254 81 1-4.016727 4.659533 0.288012 82 1-4.201662 3.307664 2.357723 83 6-4.548144 0.625392 2.496808 84 6-4.697038-0.722857 2.411413 85 1-4.488561 1.113957 3.468046 86 1-4.753781-1.330283 3.312990 ENERGY=-2071.2935781 Hartree Frequencies 14.4827 16.4392 24.4634 32.9104 34.5819 44.0857 49.0839 53.2979 64.7014 (i) coronene-1-perhydrocoronene Center Atomic Coordinates (Angstroms) Number Number X Y Z 1 6-4.690313-1.277159-0.577391 2 6-4.658045-0.136241-1.428295 3 6-4.649216 1.171432-0.864320 4 6-4.662792 1.337373 0.549977 5 6-4.695548 0.195793 1.398999 6 6-4.703568-1.112450 0.836535 7 6-1.100155-1.224299-0.729545 8 6-0.667420-1.336797 0.722813 9 6-1.111853-0.090266 1.472213 10 6-0.642104 1.213737 0.847755 11 6-1.068456 1.251839-0.611400 S18

12 6-0.624739 0.043765-1.420046 13 6-4.552947 2.304352-1.708227 14 6-4.568750-0.303107-2.831301 15 6-4.634981-2.577443-1.136824 16 6-4.658428-2.246388 1.682164 17 6-4.646826 0.359816 2.805292 18 6-4.576512 2.634810 1.110162 19 6-4.486875 3.595077-1.119701 20 6-4.496845 3.754487 0.239766 21 6-4.486068 2.108749-3.113428 22 6-4.493906 0.851463-3.654958 23 6-4.532453-1.618471-3.366009 24 6-4.565443-2.715730-2.548298 25 6-4.610677-3.698510-0.265419 26 6-4.621739-3.539104 1.093996 27 6-4.627182-2.052541 3.088882 28 6-4.623119-0.795124 3.630444 29 6-4.582809 1.673597 3.341018 30 6-4.548380 2.770949 2.523522 31 1-4.567684-4.694985-0.701453 32 1-4.520736-3.718046-2.970592 33 1-4.464519-1.739692-4.445755 34 1-4.428947 0.717115-4.733501 35 1-4.412927 2.983671-3.756973 36 1-4.409686 4.461440-1.774226 37 1-4.430890 4.749582 0.676315 38 1-4.486357 3.771605 2.948141 39 1-4.546344 1.792632 4.422428 40 1-4.583060-0.661806 4.710078 41 1-4.593836-2.928634 3.734263 42 1-4.590035-4.407708 1.749711 43 9-0.690481-0.156386 2.777347 44 9 0.692588-1.501215 0.810077 45 9 0.719947 1.336715 0.958512 46 9-0.605713 2.402056-1.201829 47 9 0.740335 0.033130-1.561279 48 1-2.215764-0.082832 1.469956 49 1-1.137180-2.221963 1.176822 50 1-1.095949 2.060509 1.383753 51 1-2.170984 1.281407-0.633594 52 1-2.203485-1.221731-0.750128 53 1-1.061803 0.097420-2.428162 54 9-0.668682-2.323494-1.430447 55 6 4.487025 3.781713 0.639112 56 6 4.000653 3.760661-0.802316 57 1 2.897588 3.808239-0.817240 S19

58 1 5.590939 3.815860 0.654378 59 6 4.510365 2.555932 2.847339 60 6 4.024414 2.547579 1.403885 61 6 4.046735 1.316815 3.599032 62 1 2.918288 2.551345 1.419274 63 1 2.944042 1.318038 3.663947 64 1 5.614142 2.596859 2.850756 65 6 4.438536 2.492009-1.524097 66 6 4.380252 1.188754-3.679161 67 6 3.948628 2.462177-2.966559 68 1 2.845821 2.524718-2.963692 69 1 5.547594 2.474014-1.540182 70 1 5.482022 1.164600-3.754445 71 6 4.458622 1.264872 0.686837 72 6 4.399670-0.037114-1.481510 73 6 4.333517-1.338009-3.636627 74 6 4.488056 0.038094 2.897386 75 6 4.430889-1.264184 0.729269 76 6 4.364308-2.565281-1.438827 77 6 4.465449-2.480115 2.933442 78 6 4.404690-3.780862 0.766597 79 6 3.975457 1.245970-0.764074 80 6 3.910994-0.053979-2.933455 81 6 4.001948 0.017503 1.445943 82 6 3.939884-1.281817-0.719265 83 6 3.862290-2.569910-2.877254 84 6 4.025498-1.207701 3.643134 85 6 3.974257-2.512230 1.492112 86 6 3.902242-3.797124-0.669543 87 1 2.866944 1.262186-0.743616 88 1 2.805657-0.034119-2.904407 89 1 2.893097 0.027290 1.466983 90 1 2.830486-1.266956-0.694107 91 1 2.758275-2.592159-2.862540 92 1 2.922992-1.187690 3.710574 93 1 2.868756-2.495025 1.512114 94 1 2.798096-3.817567-0.670069 95 1 5.571118 1.256656 0.669717 96 1 5.511945-0.053765-1.507801 97 1 5.435040-1.354835-3.717626 98 1 5.597083 0.027754 2.873253 99 1 5.543232-1.280053 0.706826 100 1 5.473360-2.576988-1.465146 101 1 5.568372-2.540598 2.936403 102 1 5.507791-3.838515 0.772037 103 1 4.187428-3.491057-3.384107 S20

104 1 3.947399-1.342787-4.667168 105 1 4.232729-4.708801-1.189792 106 1 4.045794-4.664251 1.316245 107 1 4.105213-3.370893 3.469982 108 1 4.402222-1.185438 4.677001 109 1 4.421055 1.323943 4.633888 110 1 4.165304 3.471361 3.351413 111 1 4.142305 4.691059 1.154177 112 1 4.359015 4.645426-1.350072 113 1 4.310443 3.352649-3.502577 114 1 3.999278 1.170093-4.711550 ENERGY=-2687.9070572 Hartree Frequencies -22.5825 9.1123 15.9510 19.0364 23.7185 27.4189 31.2385 36.7463 42.6678 7. Complete Reference for Gaussian 09 and Amsterdam Density Functional Theory (ADF) software package. (i) Complete Reference for Gaussian 09: Gaussian 09, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G.E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.;Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.;Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.;Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc., Wallingford CT, 2009. (ii). Complete Reference for Amsterdam Density Functional software (ADF): ADF2008.01, SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands. E.J. Baerends, J. Autschbach, A. Bérces, F.M. Bickelhaupt, C.Bo, P.M. Boerrigter, L. Cavallo, D.P. Chong, L. Deng, R.M. Dickson, D.E. Ellis, M. van Faassen, L. Fan, T. H. Fischer, C.Fonseca Guerra, S.J.A. van Gisbergen, A.W. Götz, J.A. Groeneveld, O.V. Gritsenko, M. Grüning, F.E. Harris, P. van den Hoek, C.R. Jacob, H. Jacobsen, L. Jensen, G. van Kessel, F. Kootstra, M.V. Krykunov, E. van Lenthe, D.A. McCormack, A. Michalak, J. Neugebauer, V.P. Nicu, V.P. Osinga, S. Patchkovskii, P.H.T. Philipsen, D. Post, C.C. Pye, W. Ravenek, J.I. Rodríguez, P. Ros, P.R.T. Schipper, G. Schreckenbach,J.G. Snijders, M. Solà, M. Swart, D. Swerhone, G. te Velde, P. Vernooijs, L. Versluis, L. Visscher, O. Visser, F. Wang, T.A.Wesolowski, E.M. van Wezenbeek, G. Wiesenekker, S.K. Wolff, T.K. Woo, A.L. Yakovlev, and T. Ziegler S21