Supporting information for: A. Lange, M. A. Rohrdanz, and J. M. Herbert, "Charge-transfer excited states in a pi-stacked adenine dimer, as predicted using long-range-corrected time-dependent density functional theory" ==== Gas-phase adenine dimer geometry ==== C 6.835296 -4.376410 -0.587757 N 6.863668 -3.099766 -0.105179 C 5.965084 -2.398685 -0.865397 N 5.377625 -3.115238 -1.777233 C 5.923698 -4.382804 -1.612368 N 7.555881 -5.431665 -0.152216 C 7.273739 -6.515256 -0.851233 N 6.421055 -6.666004 -1.860741 C 5.711816 -5.595906 -2.278318 H 7.436566 -2.765635 0.655299 N 4.850999 -5.741002 -3.294951 C 2.991769 -4.014545 0.323275 N 2.474231 -2.760890 0.168322 C 1.538394 -2.869204 -0.826353 N 1.421481 -4.070993 -1.308051 C 2.344666 -4.815233 -0.582836 N 3.949915 -4.402308 1.191663 C 4.205242 -5.691308 1.066417 N 3.660940 -6.579606 0.239640 C 2.704630 -6.167666 -0.619590 H 2.741853 -1.939920 0.690404 N 2.152149 -7.057612 -1.455271 H 0.951862 -2.033257 -1.177884 H 2.449360 -8.012247 -1.436879 H 1.442639 -6.767116 -2.097305 H 4.963976 -6.079842 1.729566 H 5.763355 -1.347630 -0.720527 H 4.740852 -6.632973 -3.733420 H 4.318747 -4.957311 -3.615163 H 7.811770 -7.406024 -0.562346 ========================================== ==== Adenine dimer + 27 water molecules ==== H 2.741642 -1.940127 0.690374 N 2.474428 -2.760397 0.168213 C 1.538434 -2.869069 -0.825949 N 1.421722 -4.070785 -1.308233 C 2.345115 -4.815552 -0.583159 C 2.704522 -6.167827 -0.619808 N 2.152072 -7.057283 -1.455385 N 3.660899 -6.579751 0.239366 C 4.205460 -5.691286 1.066609 N 3.950071 -4.402240 1.191729 C 2.991353 -4.014490 0.323740 H 0.951662 -2.033525 -1.177991 H 2.449435 -8.012497 -1.437348 H 1.442735 -6.767145 -2.096990 H 4.964065 -6.079751 1.729320 H 7.436609 -2.765232 0.655194 N 6.863591 -3.099885 -0.105034 C 5.965091 -2.398714 -0.865268 N 5.377256 -3.115466 -1.776991 C 5.924022 -4.382771 -1.612416 C 5.712121 -5.595567 -2.278685 N 4.850835 -5.740740 -3.294811 N 6.421126 -6.665939 -1.861179 C 7.273453 -6.515603 -0.851246 N 7.555596 -5.431945 -0.152246 C 6.835605 -4.376177 -0.587717 H 5.763232 -1.347468 -0.720187 H 4.740753 -6.633436 -3.733611 H 4.318778 -4.957234 -3.614964 H 7.811905 -7.405960 -0.562393 O 3.074097 -10.015536 -0.365550 H 3.748425 -9.613665 -0.954390 H 3.143179 -9.534758 0.464561 O -1.311998 -6.276056 -0.940008 H -2.214814 -6.649145 -1.180343 H -0.791339 -6.558155 -1.708493 O -1.340812 -3.668722 0.041470 H -2.278009 -3.994055 0.194461 H -1.048975 -4.213034 -0.609689 O 8.651490 -5.760180 2.533259 H 8.321771 -5.806275 1.565201 H 9.523138 -6.242247 2.480828 O 2.945708 -8.395966 2.150957 H 3.413947 -7.861677 1.405781 H 3.455066 -8.196603 2.924520 O 2.508798 -3.152178 3.837966 H 2.993357 -2.611558 3.200367 H 3.131590 -3.887690 4.036885 O 9.503845 -7.641798 -2.447504 H 8.591050 -7.432434 -2.508179 H 9.581291 -8.597588 -2.576768 O 6.052040 -5.426692 -6.496176 H 5.127332 -5.628681 -6.213680 H 6.599003 -5.984170 -5.892382 O 3.624909 -6.124445 -5.934264 H 2.880197 -5.601857 -6.328927 H 3.110789 -6.933007 -5.738421 O -1.313370 -1.032503 -0.799621 H -1.770850 -1.907004 -0.875470 H -1.660250 -0.539461 -1.605118 O 4.912670 -0.758027 -3.648420 H 4.918030 -0.610175 -4.615833 H 4.677611 -1.719980 -3.549793 O 8.158758 -0.190833 1.331845 H 8.183748 0.611602 0.763674 H 9.122677 -0.226472 1.433771 O 2.999017 -3.619083 -6.425699 H 2.033699 -3.483635 -6.354195 H 3.307814 -3.322274 -5.590210 O 3.857136 -1.063625 2.498488 H 4.678171 -1.271462 3.044751 H 4.073284 -0.141283 2.299533 O 7.091868 -9.288703 2.134887 H 7.997882 -9.636354 2.332948 H 6.945419 -9.476528 1.189705 O -0.058102 -7.051727 -3.404346 H -0.223550 -8.008885 -3.618003 H 0.151521 -6.699894 -4.253052 O 0.601566 -4.069465 -3.821551 H 0.381898 -3.938264 -2.885559 H -0.342670 -4.265858 -4.082528 O 0.866418 -0.467899 -3.309522 H -0.082959 -0.535154 -3.105153 H 1.111219 0.287194 -2.726997 O 4.828983 -8.803866 -2.081342 H 4.837816 -9.018199 -3.036558 H 5.410839 -8.025360 -2.085511 O 9.773567 -3.846449 -2.448839 H 10.650523 -3.434620 -2.433854 H 9.871932 -4.515730 -1.771753 O 3.252886 -3.081990 -3.690224 H 2.322877 -3.429369 -3.824735 H 3.330814 -3.135367 -2.736850 O 8.736814 -3.023752 2.425610 H 8.585387 -3.961487 2.542616 H 9.692723 -2.982422 2.239193 O 4.834333 -9.448816 -4.843933 H 5.286959 -9.432011 -5.643945 H 3.973868 -8.987897 -5.090363 O 0.603478 -0.567895 1.216065 H 0.002258 -0.696043 0.488845 H -0.017609 -0.485353 2.000233 O 7.263967 0.123864 -2.133007 H 8.014016 -0.170657 -2.679180 H 6.485432 -0.199353 -2.715748 O 5.465368 -7.762191 3.573080 H 6.096711 -8.411522 3.131946 H 5.944301 -7.573414 4.368336 O 2.852795 0.517090 -0.118662 H 3.570066 0.761302 0.465628 H 2.097715 0.292292 0.410243 ============================================ The following data are the first 25 vertical excitation energies for adenine dimer, as a function of the coefficient of Hartree-Fock exchange (C_HF). Specifically, these calculations use the functional [cf. Eq. (2) of the paper]: E_xc = E_c(PBE) + (1 - C_HF) * E_x(PBE) + C_HF * E_x(HF). State C_HF 1 2 3 4 5 1.00 6.0938 6.2506 6.4036 6.4359 7.0514 0.95 6.0450 6.2019 6.3581 6.3903 6.9401 0.90 5.9954 6.1523 6.3105 6.3422 6.8269 0.85 5.9443 6.1018 6.2606 6.2918 6.7118 0.80 5.8926 6.0505 6.2081 6.2389 6.5955 0.75 5.8389 5.9978 6.1528 6.1832 6.4766 0.70 5.7826 5.9432 6.0947 6.1242 6.3565 0.65 5.7248 5.8867 6.0341 6.0623 6.2328 0.60 5.6648 5.8283 5.9707 5.9972 6.1079 0.55 5.6017 5.7652 5.9044 5.9278 5.9802 0.50 5.5343 5.6966 5.8339 5.8464 5.8535 0.45 5.4623 5.6213 5.7145 5.7234 5.7599 0.40 5.3851 5.5315 5.5789 5.5872 5.6188 0.35 5.2944 5.3871 5.4417 5.4504 5.4791 0.30 5.1538 5.2356 5.2962 5.3069 5.3303 0.25 4.9603 5.0836 5.1488 5.1575 5.1818 0.20 4.7557 4.8925 4.9934 5.0052 5.0691 0.15 4.5485 4.6901 4.8302 4.8473 4.9592 0.10 4.3402 4.4847 4.6576 4.6830 4.8392 0.05 4.1317 4.2783 4.4590 4.5116 4.5550 0.00 3.9231 4.0717 4.1794 4.2962 4.3292 6 7 8 9 10 1.00 7.0571 7.2656 7.3102 7.4096 7.4381 0.95 6.9455 7.1686 7.2111 7.3164 7.3382 0.90 6.8320 7.0682 7.1082 7.2175 7.2365 0.85 6.7178 6.9649 7.0020 7.1167 7.1340 0.80 6.6009 6.8590 6.8927 7.0147 7.0300 0.75 6.4823 6.7502 6.7800 6.9102 6.9200 0.70 6.3630 6.6386 6.6639 6.7869 6.7940 0.65 6.2400 6.5240 6.5419 6.6277 6.6503 0.60 6.1167 6.4024 6.4090 6.4599 6.4950 0.55 5.9883 6.2296 6.2840 6.3130 6.3327 0.50 5.8628 6.0385 6.1304 6.1725 6.1902 0.45 5.7691 5.8568 5.9459 6.0430 6.0578 0.40 5.6880 5.7240 5.7674 5.9111 5.9243 0.35 5.5498 5.6190 5.6602 5.7741 5.7899 0.30 5.4126 5.5385 5.5771 5.6320 5.6526 0.25 5.3068 5.4543 5.4818 5.4982 5.5141 0.20 5.2004 5.3273 5.3647 5.3745 5.4172 0.15 5.0852 5.1727 5.1909 5.2177 5.2530 0.10 4.8653 4.9490 4.9593 5.0202 5.0616 0.05 4.6517 4.7116 4.8083 4.8549 4.8705 0.00 4.3820 4.5593 4.6330 4.6662 4.7173 11 12 13 14 15 1.00 7.4514 7.5474 7.5936 7.6288 7.7257 0.95 7.3735 7.4422 7.4918 7.5447 7.6489 0.90 7.2889 7.3273 7.3821 7.4761 7.5699 0.85 7.1843 7.2107 7.2818 7.4064 7.4871 0.80 7.0644 7.0867 7.1921 7.3196 7.3832 0.75 6.9427 6.9537 7.0969 7.1792 7.2643 0.70 6.8198 6.8307 6.9661 7.0471 7.1310 0.65 6.7083 6.7228 6.8140 6.9162 6.9970 0.60 6.6001 6.6151 6.6681 6.7564 6.8937 0.55 6.4893 6.5043 6.5291 6.5950 6.7935 0.50 6.3710 6.3883 6.4006 6.4402 6.6836 0.45 6.2397 6.2701 6.2807 6.2948 6.5426 0.40 6.1019 6.1394 6.1561 6.1687 6.3405 0.35 5.9606 5.9988 6.0350 6.0479 6.1346 0.30 5.8166 5.8575 5.9060 5.9148 5.9392 0.25 5.6655 5.7133 5.7202 5.7744 5.7976 0.20 5.4870 5.5178 5.5387 5.5635 5.5768 0.15 5.2653 5.3031 5.3378 5.3877 5.4360 0.10 5.0678 5.1813 5.2303 5.2544 5.2843 0.05 4.9100 5.0275 5.0525 5.1273 5.1458 0.00 4.7503 4.8181 4.8853 4.8890 4.9217 16 17 18 19 20 1.00 7.7523 7.8981 7.9440 7.9689 8.0871 0.95 7.6754 7.7982 7.8550 7.8717 7.9620 0.90 7.5960 7.6939 7.7336 7.7629 7.8405 0.85 7.5112 7.5576 7.5945 7.6604 7.7171 0.80 7.4011 7.4308 7.4846 7.5228 7.5997 0.75 7.3093 7.3374 7.3607 7.3788 7.4981 0.70 7.2170 7.2340 7.2401 7.2672 7.3967 0.65 7.1205 7.1243 7.1362 7.1657 7.2924 0.60 7.0083 7.0126 7.0255 7.0757 7.1507 0.55 6.8861 6.8974 6.9083 6.9605 6.9907 0.50 6.7396 6.7746 6.7809 6.7932 6.9028 0.45 6.5621 6.6430 6.6464 6.6750 6.7931 0.40 6.4236 6.5015 6.5075 6.5617 6.6168 0.35 6.2785 6.3492 6.3619 6.3974 6.4353 0.30 6.1274 6.1626 6.1764 6.1792 6.2127 0.25 5.8673 5.8759 5.9524 5.9737 6.0348 0.20 5.6630 5.6726 5.7285 5.8146 5.8523 0.15 5.5002 5.5253 5.5344 5.6526 5.6578 0.10 5.3051 5.3795 5.3891 5.4495 5.4870 0.05 5.1869 5.1894 5.2137 5.2332 5.2440 0.00 4.9799 4.9946 5.0046 5.0097 5.0377 21 22 23 24 25 1.00 8.1017 8.1448 8.2021 8.2707 8.3216 0.95 8.0136 8.0266 8.1059 8.1582 8.2182 0.90 7.9005 7.9351 7.9940 8.0431 8.1104 0.85 7.7897 7.8448 7.8765 7.9362 7.9987 0.80 7.6925 7.7384 7.7662 7.8363 7.8958 0.75 7.5935 7.6220 7.6543 7.7442 7.7918 0.70 7.4794 7.5003 7.5300 7.6592 7.6784 0.65 7.3300 7.3762 7.4074 7.5555 7.5732 0.60 7.1823 7.2545 7.2882 7.4189 7.4584 0.55 7.0641 7.1318 7.1682 7.2512 7.3258 0.50 6.9360 7.0078 7.0418 7.0611 7.1919 0.45 6.8055 6.8556 6.8808 6.9189 7.0492 0.40 6.6556 6.7153 6.7482 6.7842 6.8114 0.35 6.4952 6.5038 6.5412 6.5971 6.6114 0.30 6.2274 6.3264 6.3373 6.4389 6.4648 0.25 6.0502 6.1546 6.1724 6.2387 6.2921 0.20 5.8831 5.9757 5.9821 6.0294 6.0541 0.15 5.7062 5.7770 5.7796 5.7965 5.8179 0.10 5.4887 5.5270 5.5528 5.5763 5.5824 0.05 5.2569 5.2972 5.3111 5.3197 5.3709 0.00 5.0600 5.0875 5.0922 5.0983 5.1233 ================================================== Excitation energies for the lowest charge transfer state in the C2H4 -- C2F4 dimer at various intermolecular separations Calculations performed with TD-LRC-PBE0/6-31G* These can be compared to the SAC-CI/6-31G* benchmarks in: Y. Tawada et al., J. Chem. Phys. 120, 8425 (2004). Geometries for this calculation can be found at the end of this file. Intermolecular separation: 5 Angstroms -------------------------------------------- mu excitation energy (1/bohr) (eV) .000 8.0227 .050 8.0842 .100 8.4776 .150 8.7061 .200 9.7102 .250 10.3620 .300 10.8336 .350 11.1981 .400 11.4201 .450 11.6233 .500 11.5530 .550 11.9692 .600 12.0613 .650 12.1318 .700 12.1861 .750 12.2284 .800 12.2617 .850 12.2882 .900 12.3098 Intermolecular separation: 6 Angstroms -------------------------------------------- mu excitation energy (1/bohr) (eV) .000 8.1022 .050 8.1962 .100 8.6669 .150 9.4564 .200 10.1878 .250 10.7961 .300 11.2410 .350 11.6409 .400 11.9198 .450 12.1307 .500 12.2901 .550 12.4107 .600 12.5022 .650 12.5721 .700 12.6260 .750 12.6678 .800 12.7007 .850 12.7270 .900 12.7483 Intermolecular separation: 7 Angstroms -------------------------------------------- mu excitation energy (1/bohr) (eV) .000 8.1635 .050 8.2923 .100 8.6675 .150 9.7456 .200 10.5039 .250 11.1184 .300 11.5972 .350 11.9640 .400 12.2425 .450 12.4530 .500 12.6119 .550 12.7321 .600 12.8233 .650 12.8930 .700 12.9465 .750 12.9882 .800 13.0209 .850 13.0470 .900 13.0682 Intermolecular separation: 8 Angstroms -------------------------------------------- mu excitation energy (1/bohr) (eV) .000 8.2139 .050 8.3802 .100 8.6679 .150 9.9805 .200 10.7485 .250 11.3640 .300 11.8428 .350 12.2094 .400 12.4876 .450 12.6978 .500 12.8565 .550 12.9765 .600 13.0675 .650 13.1370 .700 13.0691 .750 13.2319 .800 13.1187 .850 13.2905 .900 13.3116 Intermolecular separation: 9 Angstroms -------------------------------------------- mu excitation energy (1/bohr) (eV) .000 8.2553 .050 8.4427 .100 9.2638 .150 10.1702 .200 10.9411 .250 11.4067 .300 12.0354 .350 12.4018 .400 12.6799 .450 12.8900 .500 13.0486 .550 13.1201 .600 13.2488 .650 13.3286 .700 13.3820 .750 13.4234 .800 13.4559 .850 13.4197 .900 13.4457 Intermolecular separation: 10 Angstroms -------------------------------------------- mu excitation energy (1/bohr) (eV) .000 8.2897 .050 8.4428 .100 9.4050 .150 10.3246 .200 11.0615 .250 11.7120 .300 12.1905 .350 12.5568 .400 12.8348 .450 13.0448 .500 13.2033 .550 13.3230 .600 13.4133 .650 13.4748 .700 13.5364 .750 13.5777 .800 13.5688 .850 13.4193 .900 13.6572 =============================================== Geometries for the C2H4 -- C2F4 calculation. The geometries of the two molecules were optimized separately using BLYP/6-31G*. The distance between them is then just controlled through the z-coordinate of the C2F4. $molecule 0 1 C1 0.670604 0.000000 0.000000 C2 -0.670604 0.000000 0.000000 H1 1.249222 0.929447 0.000000 H2 1.249222 -0.929447 0.000000 H3 -1.249222 0.929447 0.000000 H4 -1.249222 -0.929447 0.000000 C3 0.669726 0.000000 5.000000 C4 -0.669726 0.000000 5.000000 F1 1.401152 1.122634 5.000000 F2 1.401152 -1.122634 5.000000 F3 -1.401152 -1.122634 5.000000 F4 -1.401152 1.122634 5.000000 $end $molecule 0 1 C1 0.670604 0.000000 0.000000 C2 -0.670604 0.000000 0.000000 H1 1.249222 0.929447 0.000000 H2 1.249222 -0.929447 0.000000 H3 -1.249222 0.929447 0.000000 H4 -1.249222 -0.929447 0.000000 C3 0.669726 0.000000 6.000000 C4 -0.669726 0.000000 6.000000 F1 1.401152 1.122634 6.000000 F2 1.401152 -1.122634 6.000000 F3 -1.401152 -1.122634 6.000000 F4 -1.401152 1.122634 6.000000 $end $molecule 0 1 C1 0.670604 0.000000 0.000000 C2 -0.670604 0.000000 0.000000 H1 1.249222 0.929447 0.000000 H2 1.249222 -0.929447 0.000000 H3 -1.249222 0.929447 0.000000 H4 -1.249222 -0.929447 0.000000 C3 0.669726 0.000000 7.000000 C4 -0.669726 0.000000 7.000000 F1 1.401152 1.122634 7.000000 F2 1.401152 -1.122634 7.000000 F3 -1.401152 -1.122634 7.000000 F4 -1.401152 1.122634 7.000000 $end $molecule 0 1 C1 0.670604 0.000000 0.000000 C2 -0.670604 0.000000 0.000000 H1 1.249222 0.929447 0.000000 H2 1.249222 -0.929447 0.000000 H3 -1.249222 0.929447 0.000000 H4 -1.249222 -0.929447 0.000000 C3 0.669726 0.000000 8.000000 C4 -0.669726 0.000000 8.000000 F1 1.401152 1.122634 8.000000 F2 1.401152 -1.122634 8.000000 F3 -1.401152 -1.122634 8.000000 F4 -1.401152 1.122634 8.000000 $end $molecule 0 1 C1 0.670604 0.000000 0.000000 C2 -0.670604 0.000000 0.000000 H1 1.249222 0.929447 0.000000 H2 1.249222 -0.929447 0.000000 H3 -1.249222 0.929447 0.000000 H4 -1.249222 -0.929447 0.000000 C3 0.669726 0.000000 9.000000 C4 -0.669726 0.000000 9.000000 F1 1.401152 1.122634 9.000000 F2 1.401152 -1.122634 9.000000 F3 -1.401152 -1.122634 9.000000 F4 -1.401152 1.122634 9.000000 $end $molecule 0 1 C1 0.670604 0.000000 0.000000 C2 -0.670604 0.000000 0.000000 H1 1.249222 0.929447 0.000000 H2 1.249222 -0.929447 0.000000 H3 -1.249222 0.929447 0.000000 H4 -1.249222 -0.929447 0.000000 C3 0.669726 0.000000 10.00000 C4 -0.669726 0.000000 10.00000 F1 1.401152 1.122634 10.00000 F2 1.401152 -1.122634 10.00000 F3 -1.401152 -1.122634 10.00000 F4 -1.401152 1.122634 10.00000 $end