Supplementary Material (ESI) for Physical Chemistry Chemical Physics This journal is (C) The Owner Societies 2007 Table S1: Sandwich Benzene Dimer Geometry (Angstroms) Optimized at the Estimated CCSD(T)/aug-cc-pVQZ Level of Theory using Frozen Monomers (C-C=1.3915, C-H=1.0800), R(center-to-center)=3.9 Angstroms C 2.629553713 0.000000000 -3.684965678 C 1.314776857 -2.277260316 -3.684965678 C -1.314776857 -2.277260316 -3.684965678 C -2.629553713 0.000000000 -3.684965678 C -1.314776857 2.277260316 -3.684965678 C 1.314776857 2.277260316 -3.684965678 C 2.629553713 0.000000000 3.684965678 C 1.314776857 2.277260316 3.684965678 C -1.314776857 2.277260316 3.684965678 C -2.629553713 0.000000000 3.684965678 C -1.314776857 -2.277260316 3.684965678 C 1.314776857 -2.277260316 3.684965678 H 4.670457781 0.000000000 -3.684965678 H 2.335228890 -4.044735085 -3.684965678 H -2.335228890 -4.044735085 -3.684965678 H -4.670457781 0.000000000 -3.684965678 H -2.335228890 4.044735085 -3.684965678 H 2.335228890 4.044735085 -3.684965678 H 4.670457781 0.000000000 3.684965678 H 2.335228890 4.044735085 3.684965678 H -2.335228890 4.044735085 3.684965678 H -4.670457781 0.000000000 3.684965678 H -2.335228890 -4.044735085 3.684965678 H 2.335228890 -4.044735085 3.684965678 Table S2: T-Shaped Benzene Dimer Geometry (Angstroms) Optimized at the Estimated CCSD(T)/aug-cc-pVQZ Level of Theory using Frozen Monomers (C-C=1.3915, C-H=1.0800), R(center-to-center)=5.0 Angstroms C -2.629553713 0.000000000 4.724314971 C -1.314776857 2.277260316 4.724314971 C 1.314776857 2.277260316 4.724314971 C 2.629553713 0.000000000 4.724314971 C 1.314776857 -2.277260316 4.724314971 C -1.314776857 -2.277260316 4.724314971 C 0.000000000 0.000000000 -2.094761258 C 0.000000000 -2.277260316 -3.409538115 C 0.000000000 -2.277260316 -6.039091828 C 0.000000000 0.000000000 -7.353868685 C 0.000000000 2.277260316 -6.039091828 C 0.000000000 2.277260316 -3.409538115 H -4.670457781 0.000000000 4.724314971 H -2.335228890 4.044735085 4.724314971 H 2.335228890 4.044735085 4.724314971 H 4.670457781 0.000000000 4.724314971 H 2.335228890 -4.044735085 4.724314971 H -2.335228890 -4.044735085 4.724314971 H 0.000000000 0.000000000 -0.053857191 H 0.000000000 -4.044735085 -2.389086081 H 0.000000000 -4.044735085 -7.059543862 H 0.000000000 0.000000000 -9.394772752 H 0.000000000 4.044735085 -7.059543862 H 0.000000000 4.044735085 -2.389086081 Table S3: Methane-Benzene Complex Geometry (Angstroms) Optimized at the Estimated CCSD(T)/aug-cc-pVQZ Level of Theory using the Frozen Benzene Monomer (C-C=1.4057, C-H=1.0952) and the Frozen Methane Monomer (C-H=1.0995, Theta(H-C-H)=109.4712), R(center-to-center)=3.8 Angstroms C 2.656446404 0.000000000 1.223521680 C 1.328223202 -2.300550069 1.223521680 C -1.328223202 -2.300550069 1.223521680 C -2.656446404 0.000000000 1.223521680 C -1.328223202 2.300550069 1.223521680 C 1.328223202 2.300550069 1.223521680 C 0.000000000 0.000000000 -5.957437077 H 4.726093204 0.000000000 1.223521680 H 2.363046602 -4.092916775 1.223521680 H -2.363046602 -4.092916775 1.223521680 H -4.726093204 0.000000000 1.223521680 H -2.363046602 4.092916775 1.223521680 H 2.363046602 4.092916775 1.223521680 H 0.000000000 0.000000000 -3.879677683 H 1.958930483 0.000000000 -6.650023143 H -0.979465242 1.696483563 -6.650023143 H -0.979465242 -1.696483563 -6.650023143 Table S4: Hydrogen Sulfide-Benzene Complex Geometry (Angstroms) Optimized at the Estimated CCSD(T)/aug-cc-pVQZ Level of Theory using the Frozen Benzene Monomer (C-C=1.3915, C-H=1.0800) and the Frozen Hydrogen Sulfur Monomer (S-H=1.3356, Theta(H-S-H)=92.12), R(center-to-sulfur)=3.8 Angstroms C 0.000000000 2.629553713 2.149638934 C 2.277260316 1.314776857 2.149638934 C 2.277260316 -1.314776857 2.149638934 C 0.000000000 -2.629553713 2.149638934 C -2.277260316 -1.314776857 2.149638934 C -2.277260316 1.314776857 2.149638934 H 0.000000000 4.670457781 2.149638934 H 4.044735085 2.335228890 2.149638934 H 4.044735085 -2.335228890 2.149638934 H 0.000000000 -4.670457781 2.149638934 H -4.044735085 -2.335228890 2.149638934 H -4.044735085 2.335228890 2.149638934 H 0.000000000 -1.817389707 -3.279961242 H 0.000000000 1.817389707 -3.279961242 S 0.000000000 0.000000000 -5.031319823 Table S5: Mehthane Dimer Geometry (Angstroms) Optimized at the CCSD(T)/aug-cc-pVQZ Level of Theory using the Frozen Monomers (C-H=1.0995, Theta(H-C-H)=109.4712), R(center-to-center)=3.7 Angstroms C 0.000000000 0.000000000 3.590479378 C 0.000000000 0.000000000 -3.590479378 H 0.000000000 0.000000000 5.668238772 H 1.958930483 0.000000000 2.897893312 H -0.979465242 1.696483563 2.897893312 H -0.979465242 -1.696483563 2.897893312 H 0.000000000 0.000000000 -5.668238772 H -1.958930483 0.000000000 -2.897893312 H 0.979465242 -1.696483563 -2.897893312 H 0.979465242 1.696483563 -2.897893312 Table S6: Sandwich Benzene Dimer Potential Energy Curves using Various Basis Sets with the Counterpoise-corrected, CCSD(T) Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ Estd aug-cc-pVTZ Estd aug-cc-pVQZ Estd CBS ----------------------------------------------------------------------------------- 3.3 2.638 1.847 1.400 1.197 3.4 1.066 0.437 0.070 -0.094 3.5 0.015 -0.493 -0.796 -0.926 3.6 -0.660 -1.078 -1.329 -1.432 3.7 -1.067 -1.418 -1.627 -1.707 3.8 -1.287 -1.588 -1.762 -1.824 3.9 -1.379 -1.640 -1.786 -1.833 4.0 -1.386 -1.615 -1.738 -1.773 4.1 -1.339 -1.540 -1.643 -1.669 4.2 -1.259 -1.436 -1.521 -1.540 4.5 -0.949 -1.067 -1.113 -1.118 5.0 -0.499 -0.554 -0.576 -0.574 5.5 -0.234 -0.257 -0.278 -0.276 6.0 -0.095 -0.106 -0.120 -0.118 6.5 -0.027 -0.033 -0.039 -0.038 Table S7: Sandwich Benzene Dimer Potential Energy Curves using Various Basis Sets with the Counterpoise-corrected, DF-SCS-MP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.3 2.282 1.589 1.312 1.123 3.4 0.761 0.211 -0.011 -0.162 3.5 -0.247 -0.691 -0.868 -0.987 3.6 -0.886 -1.251 -1.392 -1.486 3.7 -1.263 -1.571 -1.682 -1.754 3.8 -1.457 -1.721 -1.808 -1.862 3.9 -1.527 -1.758 -1.824 -1.865 4.0 -1.516 -1.718 -1.769 -1.798 4.1 -1.453 -1.631 -1.669 -1.690 4.2 -1.359 -1.516 -1.545 -1.559 4.5 -1.020 -1.123 -1.135 -1.137 5.0 -0.543 -0.588 -0.592 -0.588 5.5 -0.262 -0.280 -0.281 -0.277 6.0 -0.113 -0.121 -0.121 -0.118 6.5 -0.039 -0.043 -0.042 -0.040 Table S8: Sandwich Benzene Dimer Potential Energy Curves using Various Basis Sets with the DF-SCS-LMP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.3 1.475 1.656 1.534 1.315 3.4 -0.016 0.248 0.176 0.004 3.5 -0.991 -0.682 -0.712 -0.847 3.6 -1.596 -1.267 -1.263 -1.367 3.7 -1.937 -1.604 -1.574 -1.654 3.8 -2.096 -1.767 -1.720 -1.780 3.9 -2.132 -1.809 -1.752 -1.797 4.0 -2.086 -1.773 -1.711 -1.744 4.1 -1.990 -1.687 -1.623 -1.647 4.2 -1.864 -1.571 -1.508 -1.525 4.5 -1.433 -1.175 -1.117 -1.125 5.0 -0.873 -0.624 -0.587 -0.589 5.5 -0.524 -0.304 -0.281 -0.281 6.0 -0.268 -0.144 -0.124 -0.125 6.5 -0.110 -0.061 -0.045 -0.046 Table S9: Sandwich Benzene Dimer Potential Energy Curves using Various Basis Sets with the Counterpoise-corrected DF-SCSN-MP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.3 2.478 1.901 1.731 1.621 3.4 0.881 0.399 0.258 0.166 3.5 -0.183 -0.595 -0.713 -0.788 3.6 -0.861 -1.222 -1.320 -1.382 3.7 -1.265 -1.589 -1.670 -1.719 3.8 -1.477 -1.771 -1.838 -1.878 3.9 -1.558 -1.827 -1.882 -1.915 4.0 -1.552 -1.799 -1.844 -1.870 4.1 -1.491 -1.717 -1.754 -1.775 4.2 -1.396 -1.602 -1.634 -1.650 4.5 -1.044 -1.194 -1.215 -1.223 5.0 -0.541 -0.625 -0.638 -0.641 5.5 -0.244 -0.291 -0.300 -0.301 6.0 -0.089 -0.119 -0.124 -0.131 6.5 -0.014 -0.035 -0.038 -0.039 Table S10: Sandwich Benzene Dimer Potential Energy Curves using Various Basis Sets with the DF-SCSN-LMP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.3 1.699 2.012 1.920 1.723 3.4 0.133 0.480 0.418 0.251 3.5 -0.899 -0.541 -0.578 -0.719 3.6 -1.546 -1.192 -1.207 -1.325 3.7 -1.919 -1.577 -1.574 -1.673 3.8 -2.101 -1.773 -1.757 -1.839 3.9 -2.151 -1.839 -1.814 -1.882 4.0 -2.114 -1.816 -1.786 -1.843 4.1 -2.021 -1.738 -1.706 -1.753 4.2 -1.894 -1.627 -1.593 -1.633 4.5 -1.444 -1.226 -1.192 -1.217 5.0 -0.871 -0.651 -0.627 -0.639 5.5 -0.520 -0.310 -0.295 -0.301 6.0 -0.252 -0.140 -0.124 -0.128 6.5 -0.089 -0.053 -0.039 -0.042 Table S11: Sandwich Benzene Dimer Potential Energy Curves using Various Basis Sets with the DF-MP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.3 -0.454 -1.254 -1.550 -1.753 3.4 -1.641 -2.277 -2.516 -2.680 3.5 -2.355 -2.870 -3.063 -3.193 3.6 -2.737 -3.161 -3.315 -3.418 3.7 -2.889 -3.245 -3.367 -3.448 3.8 -2.885 -3.190 -3.287 -3.349 3.9 -2.782 -3.047 -3.123 -3.170 4.0 -2.619 -2.852 -2.910 -2.945 4.1 -2.424 -2.628 -2.674 -2.699 4.2 -2.215 -2.395 -2.429 -2.447 4.5 -1.608 -1.728 -1.744 -1.749 5.0 -0.868 -0.922 -0.928 -0.926 5.5 -0.448 -0.471 -0.474 -0.471 6.0 -0.225 -0.236 -0.236 -0.234 6.5 -0.108 -0.114 -0.114 -0.112 Table S12: T-Shaped Benzene Dimer Potential Energy Curves using Various Basis Sets with the Counterpoise-corrected, CCSD(T)/CBS Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ Estd aug-cc-pVTZ Estd aug-cc-pVQZ Estd CBS ----------------------------------------------------------------------------------- 4.4 2.155 1.039 0.583 0.383 4.5 0.478 -0.429 -0.829 -0.992 4.6 -0.680 -1.410 -1.762 -1.895 4.7 -1.446 -2.029 -2.340 -2.449 4.8 -1.922 -2.386 -2.661 -2.750 4.9 -2.187 -2.555 -2.799 -2.871 5.0 -2.302 -2.593 -2.809 -2.868 5.1 -2.312 -2.543 -2.734 -2.782 5.2 -2.253 -2.436 -2.604 -2.644 5.3 -2.150 -2.294 -2.442 -2.475 5.4 -2.021 -2.135 -2.264 -2.291 5.5 -1.880 -1.969 -2.081 -2.104 5.6 -1.736 -1.804 -1.901 -1.919 6.0 -1.206 -1.228 -1.278 -1.287 6.5 -0.741 -0.746 -0.773 -0.777 7.0 -0.462 -0.464 -0.483 -0.486 7.5 -0.299 -0.300 -0.312 -0.314 8.0 -0.200 -0.200 -0.210 -0.211 Table S13: T-Shaped Benzene Dimer Potential Energy Curves using Various Basis Sets with the Counterpoise-corrected, DF-SCS-MP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 4.4 2.486 1.464 1.197 0.999 4.5 0.803 -0.024 -0.243 -0.405 4.6 -0.366 -1.029 -1.209 -1.340 4.7 -1.149 -1.676 -1.824 -1.931 4.8 -1.646 -2.063 -2.183 -2.270 4.9 -1.933 -2.262 -2.360 -2.431 5.0 -2.071 -2.329 -2.410 -2.468 5.1 -2.104 -2.307 -2.374 -2.421 5.2 -2.067 -2.227 -2.282 -2.320 5.3 -1.985 -2.110 -2.156 -2.187 5.4 -1.876 -1.973 -2.011 -2.037 5.5 -1.753 -1.828 -1.860 -1.881 5.6 -1.624 -1.682 -1.708 -1.726 6.0 -1.144 -1.161 -1.173 -1.182 6.5 -0.713 -0.716 -0.721 -0.725 7.0 -0.450 -0.452 -0.454 -0.457 7.5 -0.294 -0.295 -0.296 -0.298 8.0 -0.198 -0.199 -0.200 -0.201 Table S14: T-Shaped Benzene Dimer Potential Energy Curves using Various Basis Sets with the DF-SCS-LMP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 4.4 1.987 1.468 1.367 1.117 4.5 0.259 -0.038 -0.097 -0.304 4.6 -0.943 -1.055 -1.082 -1.254 4.7 -1.748 -1.710 -1.714 -1.857 4.8 -2.256 -2.101 -2.087 -2.206 4.9 -2.542 -2.302 -2.276 -2.374 5.0 -2.661 -2.371 -2.336 -2.418 5.1 -2.660 -2.350 -2.309 -2.378 5.2 -2.571 -2.271 -2.226 -2.283 5.3 -2.426 -2.156 -2.107 -2.155 5.4 -2.248 -2.021 -1.969 -2.010 5.5 -2.058 -1.877 -1.824 -1.858 5.6 -1.871 -1.731 -1.677 -1.707 6.0 -1.290 -1.199 -1.160 -1.181 6.5 -0.828 -0.742 -0.718 -0.732 7.0 -0.537 -0.468 -0.453 -0.463 7.5 -0.355 -0.306 -0.297 -0.304 Table S15: T-Shaped Benzene Dimer Potential Energy Curves using Various Basis Sets with the Counterpoised-corrected, DF-SCSN-MP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 4.4 1.286 0.549 0.435 0.350 4.5 -0.268 -0.866 -0.960 -1.030 4.6 -1.321 -1.799 -1.878 -1.935 4.7 -2.000 -2.379 -2.444 -2.491 4.8 -2.404 -2.701 -2.755 -2.794 4.9 -2.609 -2.840 -2.885 -2.917 5.0 -2.675 -2.853 -2.890 -2.916 5.1 -2.644 -2.780 -2.812 -2.833 5.2 -2.551 -2.654 -2.680 -2.698 5.3 -2.419 -2.496 -2.518 -2.533 5.4 -2.267 -2.322 -2.340 -2.353 5.5 -2.105 -2.143 -2.158 -2.169 5.6 -1.942 -1.966 -1.979 -1.987 6.0 -1.359 -1.352 -1.357 -1.361 6.5 -0.849 -0.835 -0.836 -0.838 7.0 -0.538 -0.529 -0.528 -0.529 7.5 -0.352 -0.346 -0.345 -0.346 8.0 -0.239 -0.234 -0.234 -0.234 Table S16: T-Shaped Benzene Dimer Potential Energy Curves using Various Basis Sets with the DF-SCSN-LMP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 4.4 0.703 0.590 0.573 0.383 4.5 -0.898 -0.848 -0.843 -1.004 4.6 -1.984 -1.799 -1.778 -1.914 4.7 -2.682 -2.391 -2.358 -2.474 4.8 -3.094 -2.721 -2.680 -2.779 4.9 -3.294 -2.866 -2.820 -2.904 5.0 -3.339 -2.883 -2.834 -2.905 5.1 -3.271 -2.814 -2.763 -2.824 5.2 -3.126 -2.691 -2.638 -2.690 5.3 -2.931 -2.535 -2.481 -2.526 5.4 -2.709 -2.364 -2.308 -2.346 5.5 -2.479 -2.187 -2.130 -2.162 5.6 -2.255 -2.012 -1.954 -1.982 6.0 -1.545 -1.390 -1.346 -1.363 6.5 -0.991 -0.864 -0.833 -0.843 7.0 -0.645 -0.548 -0.528 -0.533 7.5 -0.426 -0.361 -0.346 -0.350 Table S17: T-Shaped Benzene Dimer Potential Energy Curves using Various Basis Sets with the Counterpoised-corrected, DF-MP2/CBS Level Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 4.4 0.246 -0.879 -1.142 -1.335 4.5 -1.150 -2.066 -2.279 -2.436 4.6 -2.069 -2.808 -2.981 -3.108 4.7 -2.635 -3.227 -3.367 -3.470 4.8 -2.942 -3.414 -3.528 -3.610 4.9 -3.065 -3.441 -3.533 -3.599 5.0 -3.060 -3.359 -3.433 -3.486 5.1 -2.969 -3.208 -3.267 -3.309 5.2 -2.825 -3.015 -3.063 -3.097 5.3 -2.650 -2.801 -2.840 -2.866 5.4 -2.460 -2.581 -2.611 -2.632 5.5 -2.267 -2.363 -2.387 -2.403 5.6 -2.077 -2.154 -2.172 -2.184 6.0 -1.423 -1.452 -1.456 -1.459 6.5 -0.872 -0.885 -0.881 -0.879 7.0 -0.545 -0.556 -0.549 -0.545 7.5 -0.353 -0.364 -0.355 -0.350 8.0 -0.237 -0.247 -0.238 -0.232 Table S18: Methane-Benzene Complex Potential Energy Curves using Various Basis Sets with the Counterpoised-corrected, CCSD(T) Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ Estd aug-cc-pVTZ Estd aug-cc-pVQZ Estd CBS ----------------------------------------------------------------------------------- 3.2 1.781 0.98 0.811 0.690 3.3 0.668 0.027 -0.110 -0.208 3.4 -0.099 -0.611 -0.721 -0.799 3.5 -0.609 -1.016 -1.103 -1.164 3.6 -0.928 -1.250 -1.314 -1.357 3.7 -1.110 -1.366 -1.415 -1.450 3.8 -1.195 -1.399 -1.439 -1.466 3.9 -1.214 -1.376 -1.407 -1.428 4.0 -1.188 -1.318 -1.334 -1.344 4.1 -1.135 -1.239 -1.245 -1.248 4.2 -1.066 -1.149 -1.150 -1.150 4.4 -0.908 -0.959 -0.958 -0.956 4.6 -0.751 -0.784 -0.774 -0.767 4.8 -0.612 -0.633 -0.618 -0.608 5.0 -0.495 -0.508 -0.489 -0.476 5.2 -0.399 -0.407 -0.385 -0.370 5.4 -0.322 -0.327 -0.290 -0.290 5.6 -0.260 -0.263 -0.246 -0.234 6.0 -0.172 -0.174 -0.156 -0.143 Table S19: Methane-Benzene Complex Potential Energy Curves using Various Basis Sets with the Counterpoised-corrected, DF-SCS-MP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.2 2.243 1.517 1.333 1.203 3.3 1.094 0.516 0.363 0.257 3.4 0.290 -0.168 -0.294 -0.380 3.5 -0.256 -0.617 -0.721 -0.791 3.6 -0.610 -0.894 -0.980 -1.037 3.7 -0.825 -1.049 -1.120 -1.167 3.8 -0.940 -1.118 -1.177 -1.214 3.9 -0.987 -1.129 -1.177 -1.207 4.0 -0.988 -1.100 -1.140 -1.164 4.1 -0.958 -1.047 -1.079 -1.099 4.2 -0.909 -0.980 -1.007 -1.023 4.4 -0.786 -0.830 -0.848 -0.859 4.6 -0.658 -0.685 -0.697 -0.704 4.8 -0.540 -0.557 -0.565 -0.569 5.0 -0.440 -0.450 -0.455 -0.459 5.2 -0.356 -0.363 -0.367 -0.369 5.4 -0.288 -0.293 -0.296 -0.298 5.6 -0.234 -0.238 -0.240 -0.241 6.0 -0.156 -0.158 -0.160 -0.161 Table S20: Methane-Benzene Complex Potential Energy Curves using Various Basis Sets with the DF-SCS-LMP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.2 1.736 1.504 1.407 1.242 3.3 0.591 0.496 0.427 0.292 3.4 -0.203 -0.192 -0.238 -0.349 3.5 -0.730 -0.644 -0.673 -0.764 3.6 -1.059 -0.923 -0.939 -1.014 3.7 -1.243 -1.079 -1.085 -1.148 3.8 -1.321 -1.147 -1.148 -1.200 3.9 -1.325 -1.157 -1.153 -1.198 4.0 -1.281 -1.128 -1.121 -1.159 4.1 -1.206 -1.075 -1.065 -1.098 4.2 -1.116 -1.009 -0.996 -1.025 4.4 -0.930 -0.860 -0.844 -0.865 4.6 -0.767 -0.713 -0.697 -0.714 4.8 -0.639 -0.581 -0.568 -0.583 5.0 -0.536 -0.471 -0.461 -0.473 5.2 -0.449 -0.382 -0.373 -0.383 5.4 -0.373 -0.310 -0.302 -0.311 5.6 -0.306 -0.252 -0.246 -0.254 6.0 -0.203 -0.169 -0.166 -0.172 Table S21: Methane-Benzene Complex Potential Energy Curves using Various Basis Sets with the Counterpoised-corrected, DF-SCSN-MP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.2 1.643 1.084 0.998 0.940 3.3 0.557 0.110 0.036 -0.012 3.4 -0.189 -0.544 -0.607 -0.647 3.5 -0.681 -0.963 -1.017 -1.050 3.6 -0.988 -1.210 -1.257 -1.284 3.7 -1.161 -1.337 -1.376 -1.399 3.8 -1.239 -1.378 -1.412 -1.431 3.9 -1.253 -1.363 -1.392 -1.408 4.0 -1.225 -1.311 -1.335 -1.349 4.1 -1.169 -1.237 -1.257 -1.268 4.2 -1.098 -1.150 -1.167 -1.177 4.4 -0.938 -0.967 -0.979 -0.985 4.6 -0.780 -0.795 -0.803 -0.807 4.8 -0.638 -0.646 -0.651 -0.654 5.0 -0.519 -0.522 -0.525 -0.527 5.2 -0.420 -0.421 -0.423 -0.425 5.4 -0.340 -0.341 -0.342 -0.343 5.6 -0.276 -0.276 -0.277 -0.278 6.0 -0.185 -0.185 -0.185 -0.186 Table S22: Methane-Benzene Complex Potential Energy Curves using Various Basis Sets with the DF-SCSN-LMP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.2 1.091 1.082 1.045 0.925 3.3 0.010 0.098 0.076 -0.026 3.4 -0.723 -0.562 -0.574 -0.660 3.5 -1.195 -0.985 -0.989 -1.062 3.6 -1.473 -1.235 -1.233 -1.296 3.7 -1.610 -1.362 -1.357 -1.411 3.8 -1.645 -1.404 -1.397 -1.443 3.9 -1.612 -1.389 -1.380 -1.419 4.0 -1.533 -1.337 -1.326 -1.360 4.1 -1.429 -1.263 -1.249 -1.279 4.2 -1.312 -1.178 -1.161 -1.187 4.4 -1.084 -0.996 -0.976 -0.995 4.6 -0.891 -0.822 -0.803 -0.817 4.8 -0.740 -0.669 -0.653 -0.664 5.0 -0.620 -0.543 -0.528 -0.537 5.2 -0.518 -0.441 -0.427 -0.434 5.4 -0.428 -0.358 -0.346 -0.351 5.6 -0.351 -0.292 -0.281 -0.286 6.0 -0.233 -0.197 -0.189 -0.192 Table S23: Methane-Benzene Complex Potential Energy Curves using Various Basis Sets with the Counterpoised-corrected, DF-MP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.2 0.924 0.123 -0.064 -0.196 3.3 -0.054 -0.696 -0.852 -0.959 3.4 -0.710 -1.221 -1.350 -1.438 3.5 -1.125 -1.531 -1.638 -1.710 3.6 -1.367 -1.689 -1.777 -1.836 3.7 -1.484 -1.740 -1.813 -1.861 3.8 -1.514 -1.718 -1.779 -1.818 3.9 -1.488 -1.650 -1.701 -1.733 4.0 -1.424 -1.554 -1.596 -1.622 4.1 -1.339 -1.443 -1.477 -1.498 4.2 -1.243 -1.325 -1.353 -1.371 4.4 -1.043 -1.094 -1.113 -1.125 4.6 -0.856 -0.888 -0.901 -0.908 4.8 -0.694 -0.715 -0.723 -0.728 5.0 -0.560 -0.573 -0.578 -0.582 5.2 -0.451 -0.460 -0.464 -0.466 5.4 -0.364 -0.370 -0.373 -0.375 5.6 -0.294 -0.299 -0.301 -0.303 6.0 -0.196 -0.198 -0.200 -0.201 Table S24: Hydrogen Sulfide-Benzene Complex Potential Energy Curves using Various Basis Sets with the Counterpoised-corrected, CCSD(T) Method R (center-to-sulfur) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ Estd aug-cc-pVQZ Estd CBS ---------------------------------------------------------------------------------- 3.20 3.263 1.919 1.529 1.236 3.40 -0.273 -1.126 -1.387 -1.584 3.50 -1.219 -1.894 -2.108 -2.269 3.60 -1.810 -2.344 -2.517 -2.649 3.70 -2.148 -2.569 -2.710 -2.818 3.80 -2.308 -2.640 -2.754 -2.843 3.90 -2.346 -2.609 -2.700 -2.773 4.00 -2.304 -2.511 -2.585 -2.645 4.10 -2.212 -2.375 -2.433 -2.483 4.20 -2.089 -2.217 -2.263 -2.305 4.50 -1.665 -1.723 -1.746 -1.771 4.75 -1.334 -1.363 -1.376 -1.393 5.00 -1.059 -1.072 -1.079 -1.092 5.25 -0.841 -0.845 -0.850 -0.860 5.50 -0.672 -0.671 -0.675 -0.682 6.00 -0.441 -0.436 -0.439 -0.444 6.50 -0.302 -0.296 -0.298 -0.301 7.00 -0.214 -0.209 -0.210 -0.212 7.50 -0.156 -0.152 -0.152 -0.154 Table S25: Hydrogen Sulfide-Benzene Complex Potential Energy Curves using Various Basis Sets with the Counterpoised-corrected, DF-SCS-MP2 Method R (center-to-sulfur) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.20 3.497 2.275 1.875 1.582 3.40 -0.042 -0.814 -1.083 -1.279 3.50 -1.000 -1.608 -1.828 -1.988 3.60 -1.606 -2.083 -2.263 -2.395 3.70 -1.960 -2.334 -2.482 -2.589 3.80 -2.137 -2.431 -2.551 -2.639 3.90 -2.193 -2.423 -2.520 -2.593 4.00 -2.168 -2.347 -2.426 -2.487 4.10 -2.091 -2.230 -2.295 -2.345 4.20 -1.984 -2.091 -2.143 -2.185 4.50 -1.597 -1.641 -1.669 -1.695 4.75 -1.290 -1.307 -1.323 -1.341 5.00 -1.031 -1.034 -1.044 -1.058 5.25 -0.824 -0.820 -0.827 -0.838 5.50 -0.663 -0.655 -0.660 -0.669 6.00 -0.440 -0.430 -0.433 -0.439 6.50 -0.303 -0.294 -0.296 -0.300 7.00 -0.217 -0.208 -0.210 -0.213 7.50 -0.159 -0.152 -0.153 -0.155 Table S26: Hydrogen Sulfide-Benzene Complex Potential Energy Curves using Various Basis Sets with the DF-SCS-LMP2 Method R (center-to-sulfur) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.20 3.457 2.444 2.117 1.768 3.40 -0.141 -0.682 -0.905 -1.155 3.50 -1.109 -1.492 -1.674 -1.883 3.60 -1.716 -1.978 -2.130 -2.308 3.70 -2.065 -2.240 -2.367 -2.520 3.80 -2.231 -2.348 -2.453 -2.584 3.90 -2.273 -2.353 -2.438 -2.550 4.00 -2.232 -2.292 -2.356 -2.452 4.10 -2.141 -2.189 -2.236 -2.317 4.20 -2.022 -2.061 -2.093 -2.163 4.50 -1.631 -1.630 -1.640 -1.687 4.75 -1.343 -1.299 -1.305 -1.340 5.00 -1.098 -1.029 -1.032 -1.058 5.25 -0.889 -0.819 -0.818 -0.838 5.50 -0.715 -0.656 -0.653 -0.669 6.00 -0.468 -0.440 -0.428 -0.434 6.50 -0.317 -0.302 -0.292 -0.294 7.00 -0.225 -0.212 -0.205 -0.206 7.50 -0.164 -0.154 -0.149 -0.148 Table S27: Hydrogen Sulfide-Benzene Complex Potential Energy Curves using Various Basis Sets with the Counterpoised-corrected, DF-SCSN-MP2 Method R (center-to-sulfur) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.20 2.259 1.415 1.252 1.133 3.40 -1.006 -1.539 -1.652 -1.734 3.50 -1.852 -2.271 -2.365 -2.432 3.60 -2.362 -2.689 -2.766 -2.822 3.70 -2.632 -2.887 -2.950 -2.996 3.80 -2.737 -2.934 -2.985 -3.022 3.90 -2.730 -2.881 -2.921 -2.952 4.00 -2.650 -2.764 -2.796 -2.821 4.10 -2.525 -2.610 -2.634 -2.655 4.20 -2.375 -2.436 -2.454 -2.471 4.50 -1.888 -1.901 -1.907 -1.916 4.75 -1.520 -1.513 -1.513 -1.519 5.00 -1.214 -1.198 -1.196 -1.200 5.25 -0.971 -0.952 -0.949 -0.952 5.50 -0.782 -0.762 -0.759 -0.761 6.00 -0.521 -0.502 -0.499 -0.500 6.50 -0.361 -0.344 -0.342 -0.342 7.00 -0.258 -0.245 -0.243 -0.243 7.50 -0.190 -0.179 -0.177 -0.178 Table S27: Hydrogen Sulfide-Benzene Complex Potential Energy Curves using Various Basis Sets with the DF-SCSN-LMP2 Method R (center-to-sulfur) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.20 2.091 1.519 1.396 1.198 3.40 -1.220 -1.460 -1.547 -1.698 3.50 -2.068 -2.205 -2.274 -2.402 3.60 -2.570 -2.631 -2.689 -2.798 3.70 -2.824 -2.837 -2.884 -2.978 3.80 -2.907 -2.892 -2.929 -3.011 3.90 -2.873 -2.848 -2.875 -2.945 4.00 -2.766 -2.741 -2.757 -2.817 4.10 -2.616 -2.596 -2.601 -2.653 4.20 -2.446 -2.430 -2.426 -2.471 4.50 -1.939 -1.906 -1.892 -1.920 4.75 -1.589 -1.518 -1.504 -1.525 5.00 -1.299 -1.204 -1.191 -1.206 5.25 -1.054 -0.960 -0.945 -0.956 5.50 -0.848 -0.771 -0.756 -0.765 6.00 -0.556 -0.514 -0.499 -0.502 6.50 -0.380 -0.354 -0.342 -0.344 7.00 -0.271 -0.250 -0.243 -0.244 7.50 -0.199 -0.182 -0.177 -0.178 Table S28: Hydrogen Sulfide-Benzene Complex Potential Energy Curves using Various Basis Sets with the Counterpoise-corrected, DF-MP2 Method R (center-to-sulfur) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.20 1.313 -0.067 -0.467 -0.761 3.40 -1.672 -2.560 -2.830 -3.027 3.50 -2.409 -3.116 -3.338 -3.499 3.60 -2.825 -3.388 -3.569 -3.701 3.70 -3.016 -3.463 -3.611 -3.720 3.80 -3.054 -3.408 -3.529 -3.618 3.90 -2.989 -3.271 -3.369 -3.442 4.00 -2.860 -3.083 -3.163 -3.224 4.10 -2.695 -2.871 -2.935 -2.986 4.20 -2.511 -2.648 -2.700 -2.742 4.50 -1.951 -2.013 -2.041 -2.066 4.75 -1.547 -1.576 -1.592 -1.609 5.00 -1.220 -1.231 -1.240 -1.253 5.25 -0.965 -0.966 -0.972 -0.982 5.50 -0.769 -0.765 -0.769 -0.777 6.00 -0.503 -0.494 -0.497 -0.502 6.50 -0.342 -0.334 -0.335 -0.338 7.00 -0.242 -0.234 -0.235 -0.237 7.50 -0.176 -0.169 -0.170 -0.172 Table S29: Methane Dimer Potential Energy Curves using Various Basis Sets with the Counterpoise-corrected, CCSD(T) Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.2 0.484 0.184 0.116 0.069 3.3 0.079 -0.150 -0.203 -0.239 3.4 -0.173 -0.348 -0.389 -0.417 3.5 -0.320 -0.453 -0.485 -0.508 3.6 -0.397 -0.499 -0.524 -0.541 3.7 -0.428 -0.505 -0.525 -0.539 3.8 -0.429 -0.489 -0.504 -0.515 3.9 -0.413 -0.459 -0.471 -0.480 4.0 -0.387 -0.422 -0.432 -0.439 4.1 -0.356 -0.383 -0.390 -0.396 4.2 -0.323 -0.344 -0.350 -0.354 4.3 -0.291 -0.306 -0.311 -0.315 4.4 -0.259 -0.272 -0.276 -0.279 4.6 -0.204 -0.213 -0.215 -0.217 4.8 -0.160 -0.165 -0.167 -0.168 5.0 -0.125 -0.129 -0.130 -0.130 5.4 -0.077 -0.079 -0.080 -0.080 5.8 -0.049 -0.050 -0.050 -0.050 Table S30: Methane Dimer Potential Energy Curves using Various Basis Sets with the Counterpoise-corrected, DF-SCS-MP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.2 0.906 0.665 0.592 0.546 3.3 0.447 0.266 0.210 0.174 3.4 0.147 0.012 -0.032 -0.060 3.5 -0.042 -0.143 -0.178 -0.199 3.6 -0.155 -0.231 -0.259 -0.276 3.7 -0.219 -0.275 -0.297 -0.310 3.8 -0.248 -0.291 -0.308 -0.318 3.9 -0.257 -0.288 -0.302 -0.310 4.0 -0.251 -0.275 -0.286 -0.293 4.1 -0.238 -0.256 -0.265 -0.270 4.2 -0.221 -0.235 -0.241 -0.245 4.3 -0.202 -0.213 -0.218 -0.221 4.4 -0.183 -0.191 -0.195 -0.197 4.6 -0.146 -0.152 -0.154 -0.156 4.8 -0.116 -0.119 -0.121 -0.122 5.0 -0.091 -0.094 -0.095 -0.095 5.4 -0.057 -0.058 -0.058 -0.059 5.8 -0.037 -0.037 -0.037 -0.037 Table S31: Methane Dimer Potential Energy Curves using Various Basis Sets with the DF-SCS-LMP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.2 0.595 0.715 0.621 0.551 3.3 0.156 0.302 0.232 0.177 3.4 -0.124 0.037 -0.015 -0.058 3.5 -0.292 -0.126 -0.165 -0.198 3.6 -0.384 -0.221 -0.250 -0.276 3.7 -0.423 -0.269 -0.292 -0.312 3.8 -0.427 -0.288 -0.305 -0.322 3.9 -0.410 -0.288 -0.301 -0.315 4.0 -0.380 -0.276 -0.287 -0.298 4.1 -0.345 -0.258 -0.267 -0.276 4.2 -0.309 -0.238 -0.244 -0.252 4.3 -0.274 -0.216 -0.221 -0.228 4.4 -0.243 -0.195 -0.199 -0.204 4.6 -0.191 -0.155 -0.158 -0.162 4.8 -0.153 -0.123 -0.124 -0.127 5.0 -0.123 -0.097 -0.098 -0.099 5.4 -0.078 -0.061 -0.061 -0.062 5.8 -0.051 -0.040 -0.039 -0.039 Table S32: Methane Dimer Potential Energy Curves using Various Basis Sets with the Counterpoise-corrected, DF-SCSN-MP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.2 0.817 0.621 0.576 0.550 3.3 0.365 0.216 0.180 0.158 3.4 0.073 -0.041 -0.070 -0.088 3.5 -0.109 -0.196 -0.220 -0.235 3.6 -0.216 -0.283 -0.303 -0.315 3.7 -0.272 -0.325 -0.341 -0.351 3.8 -0.296 -0.337 -0.350 -0.358 3.9 -0.299 -0.331 -0.342 -0.349 4.0 -0.289 -0.314 -0.323 -0.329 4.1 -0.272 -0.292 -0.299 -0.304 4.2 -0.251 -0.267 -0.273 -0.276 4.3 -0.229 -0.241 -0.246 -0.249 4.4 -0.206 -0.216 -0.220 -0.223 4.6 -0.165 -0.172 -0.175 -0.176 4.8 -0.130 -0.135 -0.137 -0.138 5.0 -0.103 -0.106 -0.107 -0.108 5.4 -0.065 -0.066 -0.067 -0.067 5.8 -0.042 -0.042 -0.042 -0.043 Table S33: Methane Dimer Potential Energy Curves using Various Basis Sets with the DF-SCSN-LMP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.2 0.587 0.668 0.592 0.534 3.3 0.149 0.253 0.192 0.144 3.4 -0.128 -0.012 -0.061 -0.101 3.5 -0.295 -0.174 -0.213 -0.246 3.6 -0.384 -0.266 -0.298 -0.325 3.7 -0.421 -0.312 -0.338 -0.361 3.8 -0.424 -0.328 -0.349 -0.368 3.9 -0.406 -0.324 -0.342 -0.358 4.0 -0.377 -0.310 -0.324 -0.338 4.1 -0.342 -0.289 -0.301 -0.313 4.2 -0.307 -0.265 -0.275 -0.285 4.3 -0.273 -0.241 -0.249 -0.257 4.4 -0.242 -0.217 -0.223 -0.230 4.6 -0.191 -0.173 -0.178 -0.183 4.8 -0.153 -0.137 -0.140 -0.144 5.0 -0.122 -0.108 -0.110 -0.113 5.4 -0.077 -0.068 -0.069 -0.070 5.8 -0.050 -0.044 -0.044 -0.045 Table S33: Methane Dimer Potential Energy Curves using Various Basis Sets with the Counterpoised-corrected, DF-MP2 Method R (center-to-center) Binding Energy (kcal/mol) (Angstroms) aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ Estd. CBS ---------------------------------------------------------------------------------- 3.2 0.543 0.261 0.184 0.135 3.3 0.134 -0.080 -0.140 -0.179 3.4 -0.122 -0.284 -0.332 -0.362 3.5 -0.274 -0.397 -0.435 -0.459 3.6 -0.356 -0.449 -0.479 -0.498 3.7 -0.391 -0.462 -0.486 -0.501 3.8 -0.397 -0.452 -0.471 -0.483 3.9 -0.386 -0.427 -0.442 -0.452 4.0 -0.363 -0.395 -0.407 -0.414 4.1 -0.335 -0.359 -0.369 -0.375 4.2 -0.305 -0.324 -0.332 -0.336 4.3 -0.275 -0.290 -0.296 -0.300 4.4 -0.246 -0.258 -0.263 -0.266 4.6 -0.195 -0.203 -0.206 -0.208 4.8 -0.153 -0.158 -0.160 -0.161 5.0 -0.120 -0.124 -0.125 -0.126 5.4 -0.075 -0.077 -0.077 -0.077 5.8 -0.048 -0.049 -0.049 -0.049