Intramolecular Competition in the Photodissociation of C3D3 Radicals at 248 and 193 nm Luca Castiglioni, Sinisa Vukovic, Paul E. Crider, William A. Lester and Daniel M. Neumark Department of Chemistry, University of California, Berkeley, CA 94720, USA and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley CA 94720, USA CONTENTS Energies, thermodynamic data and energies for: 1 D2CCCD 2 2 D3CCC 3 3 D2CDCC 4 4 DCDCDC 5 5a D2 6 5b linear DCCC 7 5b ring DCCC 8 6a D3C 9 6b singlet C2 10 6b triplet C2 11 7a D2C (triplet) 12 7b DCC 13 8a DC 14 8b DCCD 15 ts_1 1-->3 D2CCCD --> D2CDCC 16 ts_2 2-->3 D3CCC --> D2CDCC 17 ts_3 1-->5a+5b D2CCCD --> D2 + DCCC 18 ts_4 3-->5a+5b D3CCC --> D2 DCCC 19 ts_5 1-->4 D2CCCD --> DCDCDC 20 SUMMARY of RELATIVE FREE ENERGIES 21 SUMMARY of ABSOLUTE ENTHALPY ENERGIES 22 SUMMARY of ZPVE and ENTROPY 23 ============================================ 1 D2CCCD ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -115.6606440 CCSD(T)/cc-pVTZ -115.7768777 CCSD(T)/cc-pVQZ -115.8093866 CCSD(T)/CBC -115.822010 data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -115.9796763 ZPVE [Hartree] 0.033706 entropy [cal/molK] 64.207 Geometry C -0.000000 0.000129 -1.244397 C 0.000000 0.000000 0.118682 C 0.000001 -0.000144 1.326128 H -0.000001 0.922337 -1.791226 H -0.000001 -0.921987 -1.791384 H 0.000001 -0.000259 2.380134 Frequencies 322.8612 359.7297 449.3992 551.2175 578.4378 874.1783 957.3245 1216.4727 1953.0433 2346.2363 2481.0093 2705.1177 ============================================ 2 D3CCC ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -115.6021656 CCSD(T)/cc-pVTZ -115.7142457 CCSD(T)/cc-pVQZ -115.7463501 CCSD(T)/CBC -115.759237 data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -115.9090343 ZPVE [Hartree] 0.035965 entropy [cal/molK] 63.915 Geometry C 0.000007 0.000005 1.116380 C -0.000006 0.000005 -0.337326 C -0.000003 -0.000009 -1.527182 H 0.990357 -0.213081 1.496263 H -0.310644 0.964213 1.496257 H -0.679702 -0.751136 1.496247 Frequencies 272.9916 273.0965 845.5380 845.5978 878.2668 1100.1467 1100.1991 1170.9918 2241.9607 2335.2382 2361.3680 2361.3879 ============================================ 3 D2CDCC ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -115.5907755 CCSD(T)/cc-pVTZ -115.7010035 CCSD(T)/cc-pVQZ -115.7324513 CCSD(T)/CBS -115.745004 data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -115.9056036 ZPVE [Hartree] 0.032502 entropy [cal/molK] 64.776 Geometry C -1.111928 -0.139655 -0.000000 C 0.200301 0.304621 0.000001 C 1.383284 -0.289001 -0.000002 H -1.334785 -1.186933 0.000008 H -1.923486 0.557293 -0.000013 H 0.428327 1.373854 0.000008 Frequencies 220.8910 384.6866 562.7138 656.7957 660.0064 915.8672 1003.3736 1238.8706 1490.9623 2265.9674 2360.4566 2506.0352 ============================================ 4 DCDCDC ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -115.5365084 CCSD(T)/cc-pVTZ -115.6465571 CCSD(T)/cc-pVQZ -115.6780501 CCSD(T)/CBS -115.690676 data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -115.8610235 ZPVE [Hartree] 0.034189 entropy [cal/molK] 63.425 Geometry C -1.268776 -0.214275 0.000000 C -0.000508 0.472353 0.000000 C 1.079958 -0.273195 0.000000 H -1.046490 -1.286291 0.000000 H 0.033028 1.552333 0.000000 H 2.149421 -0.175339 0.000000 Frequencies 327.5955 485.3544 540.0605 703.1776 803.3297 851.5657 1240.7740 1250.3583 1975.1843 2152.3129 2335.4230 2342.2990 ============================================ 5a D2 ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -1.16325286 CCSD(T)/cc-pVTZ -1.17230883 CCSD(T)/cc-pVQZ -1.17377503 CCSD(T)/CBS -1.174058 data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -1.170606 ZPVE [Hartree] 0.007273 entropy [cal/molK] 34.537 Geometry H 0.000000 0.368101 0.000000 H 0.000000 -0.368101 0.000000 Frequencies 3192.4734 ============================================ 5b linear DCCC ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -114.3521858 CCSD(T)/cc-pVTZ -114.4549374 CCSD(T)/cc-pVQZ -114.4846553 CCSD(T)/CBS -114.496748 data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -114.654733 ZPVE [Hartree] 0.015319 entropy [cal/molK] 53.411 Geometry C 0.000782 0.000000 1.415331 C -0.000325 0.000000 0.087540 C -0.001845 0.000000 -1.137292 H 0.008326 0.000000 -2.193476 Frequencies 158.9964 388.4892 458.4949 1173.8319 1863.4032 2680.9902 ============================================ 5b ring DCCC ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -114.3515412 CCSD(T)/cc-pVTZ -114.4562684 CCSD(T)/cc-pVQZ -114.4877746 CCSD(T)/CBS data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -114.656803 ZPVE [Hartree] 0.016864 entropy [cal/molK] 59.530 Geometry C -0.000156 0.689694 0.000000 C -0.666308 -0.533829 0.000000 C 0.681723 -0.448466 0.000000 H -0.091556 1.755605 0.000000 Frequencies 534.3479 729.4599 740.3508 1248.3496 1646.7088 2503.4015 ============================================ 6a D3C ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -39.44340558 CCSD(T)/cc-pVTZ -39.49809382 CCSD(T)/cc-pVQZ -39.51221997 CCSD(T)/CBS -39.776198 data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -39.831842 ZPVE [Hartree] 0.022410 entropy [cal/molK] 53.036 Geometry C 0.000000 0.000000 0.000000 H 1.070000 0.000000 0.000000 H -0.535000 0.000000 0.926647 H -0.535000 0.000000 -0.926647 Frequencies 412.1774 1072.7421 1072.9195 2256.6400 2511.0274 2511.3493 ============================================ 6b singlet C2 ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -75.72620382 CCSD(T)/cc-pVTZ -75.78290438 CCSD(T)/cc-pVQZ -75.80071873 CCSD(T)/CBS -75.795236 data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -75.843089 ZPVE [Hartree] 0.004368 entropy [cal/molK] 45.468 Geometry C 0.000000 0.618586 0.000000 C 0.000000 -0.618586 0.000000 Frequencies 1917.4285 ============================================ 6b triplet C2 ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -75.40281844 CCSD(T)/cc-pVTZ -75.44963838 CCSD(T)/cc-pVQZ -75.46425221 CCSD(T)/CBS data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -75.898059 ZPVE [Hartree] 0.036917 entropy [cal/molK] 47.815 Geometry C 0.000000 0.000000 -0.644264 C 0.000000 0.000000 0.644264 Frequencies 1759.1979 ============================================ 7a D2C (triplet) ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -38.55189061 CCSD(T)/cc-pVTZ -38.62149769 CCSD(T)/cc-pVQZ -38.67818439 CCSD(T)/CBS -39.087719 data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -39.147659 ZPVE [Hartree] 0.013004 entropy [cal/molK] 49.029 Geometry C 0.000000 0.103364 0.000000 H 0.986276 -0.310091 0.000000 H -0.986276 -0.310091 0.000000 Frequencies 828.7321 2293.8641 2585.3575 ============================================ 7b DCC ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -76.39617674 CCSD(T)/cc-pVTZ -76.46654871 CCSD(T)/cc-pVQZ -76.48676607 CCSD(T)/CBS -76.495420 data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -76.593476 ZPVE [Hartree] 0.013024 entropy [cal/molK] 50.673 Geometry C 0.000000 -0.466894 0.000000 H 0.000000 -1.522706 0.000000 C 0.000000 0.720678 0.000000 Frequencies 475.9458 475.9458 2009.2769 2755.7246 ============================================ 8a DC ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -38.26080686 CCSD(T)/cc-pVTZ -38.29415509 CCSD(T)/cc-pVQZ -38.30364202 CCSD(T)/CBS -38.420490 data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -38.479211 ZPVE [Hartree] 0.004934 entropy [cal/molK] 43.708 Geometry C 0.000000 0.158477 0.000000 H 0.000000 -0.950862 0.000000 Frequencies 2165.9594 ============================================ 8b DCCD ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -77.10619394 CCSD(T)/cc-pVTZ -77.18634193 CCSD(T)/cc-pVQZ -77.20830976 CCSD(T)/CBS -77.217584 data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -77.314359 ZPVE [Hartree] 0.022240 entropy [cal/molK] 49.196 Geometry C 0.000000 0.592450 0.000000 H 0.000000 1.647185 0.000000 C 0.000000 -0.592450 0.000000 H 0.000000 -1.647185 0.000000 Frequencies 594.2331 594.2331 610.0819 610.0819 1890.4714 2568.7772 2894.2684 ============================================ ts_1 1-->3 D2CCCD --> D2CDCC ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -115.5900409 CCSD(T)/cc-pVTZ -115.7017022 CCSD(T)/cc-pVQZ -115.7333993 CCSD(T)/CBS -115.745963 data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -115.9040026 ZPVE [Hartree] 0.030930 entropy [cal/molK] 63.236 Geometry C -0.000000 1.177817 -0.061641 C 0.000003 -0.188540 0.100250 C -0.000003 -1.443076 -0.182575 H 0.000004 1.588898 -1.050043 H -0.000009 1.836711 0.780339 H 0.000005 -0.702818 1.133498 Frequencies -219.8689 365.1064 473.9586 546.7998 568.3803 911.7721 956.6804 1208.3796 1722.3396 1947.9037 2364.1548 2511.2609 ============================================ ts_2 2-->3 D3CCC --> D2CDCC ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -115.5359491 CCSD(T)/cc-pVTZ -115.6495857 CCSD(T)/cc-pVQZ -115.6819727 CCSD(T)/CBS -115.694883 data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -115.8475669 ZPVE [Hartree] 0.029831 entropy [cal/molK] 64.890 Geometry C -0.057226 1.157125 -0.000004 C -0.080586 -0.243964 -0.000015 C -0.023780 -1.508786 -0.000000 H -0.034427 1.699610 -0.925825 H -0.034551 1.699598 0.925827 H 1.038529 0.174547 0.000103 Frequencies -1135.1184 222.3636 319.3633 393.7709 643.6041 854.2637 961.0924 1168.9236 1739.5162 1982.7952 2326.6615 2481.9625 ============================================ ts_3 1-->5a+5b D2CCCD --> D2 + DCCC ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -115.5032949 CCSD(T)/cc-pVTZ -115.6166450 CCSD(T)/cc-pVQZ -115.6488515 CCSD(T)/CBS -115.661635 data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -115.8139893 ZPVE [Hartree] 0.026087 entropy [cal/molK] 67.306 Geometry C 0.000002 -1.198028 -0.396954 C -0.000001 0.113279 -0.035359 C 0.000000 1.322670 0.066202 H -0.000015 -2.143132 0.707368 H 0.000005 2.373778 0.156444 H 0.000010 -1.658170 1.332855 Frequencies -518.9577 242.9735 255.7158 334.1572 414.4853 501.8246 626.9353 797.9084 1131.8763 1891.4566 2561.6116 2691.9851 ============================================ ts_4 3-->5a+5b D3CCC --> D2 DCCC ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -115.4791172 CCSD(T)/cc-pVTZ -115.5920748 CCSD(T)/cc-pVQZ -115.6244444 CCSD(T)/CBS -115.637445 data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -115.7925857 ZPVE [Hartree] 0.027082 entropy [cal/molK] 66.271 Geometry C -0.075449 -0.980507 -0.235972 C 0.011553 0.292920 -0.055511 C 0.010393 1.562685 0.087791 H 0.429120 -1.739895 1.105028 H 0.254236 -1.763061 -0.876132 H -0.362338 -1.747632 0.993257 Frequencies -936.8768 208.1334 301.9842 413.3310 517.4330 620.9158 702.2870 936.5551 1222.6935 1911.8507 2503.3769 ============================================ ts_5 1-->4 D2CCCD --> DCDCDC ============================================ calculated energy at [Hartree] CCSD(T)/cc-pVDZ -115.5211235 CCSD(T)/cc-pVTZ -115.6342295 CCSD(T)/cc-pVQZ -115.6663998 CCSD(T)/CBS -115.679187 data for BHandHLYP(tight)/aug-cc-pVQZ energy [Hartree] -115.8367455 ZPVE [Hartree] 0.029308 entropy [cal/molK] 63.926 Geometry C -0.141624 1.300943 -0.212012 C -0.008101 -0.027256 0.116065 C 0.029129 -1.304418 0.020492 H 0.785800 1.849486 -0.051166 H -0.098208 0.456741 1.162681 H 0.035983 -2.121841 -0.658789 Frequencies -564.2177 339.1502 422.7793 441.0121 593.0082 734.0155 797.0715 1065.8952 1705.2106 1916.0018 2295.1099 2555.5108 +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SUMMARY of RELATIVE ENERGIES H D dG at 100K [kcal/mol] BHandHLYP CCSD(T) CCSD(T) CCSD(T) CCSD(T) CCSD(T) aug-cc-PVQZ cc-PVXZ cc-PVXZ cc-PVQZ cc-PVTZ cc-PVDZ 1 0.00 0.00 0.00 0.00 0.00 0.00 2 45.35 41.41 40.84 41.57 41.32 38.71 3 45.23 47.70 47.51 47.65 46.99 43.22 4 78.90 82.07 81.73 82.07 81.44 77.55 5a+5b_linear 85.06 83.59 85.53 83.43 82.60 79.82 6a+6b_singlet 148.17 149.13 149.46 148.50 145.65 133.66 7a+7b 140.60 140.81 141.53 140.11 138.23 131.55 8a+8b 109.22 107.86 108.45 107.16 105.76 101.89 ts1 45.64 44.28 46.07 44.25 43.74 40.87 ts2 79.82 76.69 77.27 76.87 76.79 75.16 ts3 97.54 94.20 95.55 94.30 94.11 92.31 ts4 111.69 110.40 111.45 110.64 110.55 108.49 ts5 86.28 86.22 86.89 86.32 86.11 84.14 +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SUMMARY of ABSOLUTE ENERGIES H dH at 100K [Hartree] BHandHLYP CCSD(T) CCSD(T) CCSD(T) aug-cc-PVQZ cc-PVQZ cc-PVTZ cc-PVDZ 1 -115.9796763 -115.809387 -115.776878 -115.660644 2 -115.9090343 -115.746350 -115.714246 -115.602166 3 -115.9056036 -115.732451 -115.701004 -115.590776 4 -115.8610235 -115.678050 -115.646557 -115.536508 5a -1.170606 -1.173775 -1.172309 -1.163253 5b_linear -114.654733 -114.484655 -114.454937 -114.352186 5b_ring -114.656803 -114.487775 -114.456268 -114.351541 6a -39.831842 -39.772329 -39.760819 -39.715064 6b_singlet -75.843089 -75.787482 -75.771028 -75.719660 6b_triplet -75.898059 -75.795690 -75.779048 -75.725042 7a -39.147659 -39.084411 -39.074928 -39.038260 7b -76.593476 -76.487212 -76.467181 -76.398265 8a -38.479211 -38.417372 -38.408836 -38.376929 8b -77.314359 -77.209199 -77.187451 -77.109297 ts1 -115.9040026 -115.733399 -115.701702 -115.590041 ts2 -115.8475669 -115.681973 -115.649586 -115.535949 ts3 -115.8139893 -115.648852 -115.616645 -115.503295 ts4 -115.7925857 -115.624444 -115.592075 -115.479117 ts5 -115.8367455 -115.666400 -115.634230 -115.521124 +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SUMMARY of ZPVE and ENTROPY dG at 100K [kcal/mol] at BHandHLYP/aug-cc-PVQZ H D entropy ZPVE entropy ZPVE cal/molK Hartree cal/molK Hartree 1 61.561 0.042368 64.207 0.033706 2 62.103 0.045670 63.915 0.035965 3 62.543 0.041530 64.776 0.032502 4 62.460 0.041966 64.609 0.032680 5a 31.097 0.010282 34.537 0.007273 5b linear 52.133 0.017539 53.411 0.015319 5b ring 58.810 0.019864 59.530 0.016864 6a 49.979 0.030475 53.036 0.022410 6b singlet 45.468 0.004368 45.468 0.004368 6b triplet 47.815 0.036917 47.815 0.004008 7a 46.590 0.017684 49.029 0.013004 7b 49.628 0.015725 50.673 0.013024 8a 42.258 0.006721 43.708 0.004934 8b 47.472 0.028086 49.196 0.022240 ts1 61.732 0.036917 63.236 0.030930 ts2 62.660 0.037628 64.890 0.029831 ts3 64.232 0.032542 67.306 0.026087 ts4 63.657 0.034071 66.271 0.027082 ts5 61.432 0.036917 63.926 0.029308 +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++