The Mechanism and Kinetic Analysis of C4H4+C4H4 (But-1-ene-3-yne) Reaction with Features of H-transfer in

Combustion

Peng Liu, He Lin, Zhenwu He, Yiran Zhang, Bin Guan, Zhen Huang

Key Laboratory for Power Machinery and Engineering of Ministry of Education, School of Mechanical Engineering,

Shanghai Jiao Tong University, Shanghai 200240, China

The following information is provided in this supplementary material:

T1 diagnostic

Table S1. T1 diagnostic for all structures involved in C4H4+C4H4 reaction.

Table S2. Comparison of the CASPT2 and CSB-QB3 energies for structures with multireference character, relative to structure 4.

Table S3. Total energies, relative energies, zero-point energies, expectation values of S2 operator (projected values are in parentheses), vibrational frequencies,

rotational constants, external symmetry number, optical isomers, electronic ground state, Lennard-Jones parameters for all optimized structures at B3LYP/6-

311+G(d,p) level in this work.

Table S4. Cartesian coordinates of optimized structures at B3LYP/6-311+G(d,p) level.

Table S5. Quantum chemical parameters for phenyl+acetylene reaction.

Table S6. Cartesian coordinates of optimized structures at B3LYP/6-311+G(d,p) level for phenyl+acetylene reaction.

Reference.

1

T1 diagnostic

The T1 diagnostics were performed at CCSD(T)/6-311+G(d,p) level [1] with DFT/B3LYP/6-311+G(d,p) geometries to assess whether the single-determinant

reference state CBS-QB3 method is suitable. A large T1 value suggests that the multireference electron correlation procedure is needed, and the threshold value

of T1 is considered as 0.02 for the closed-shell system.[2] The ZPE of some structures with multireference feature were recalculated at CASPT2(8,8)/B3LYP/6-

311+G(d,p) [3] level with the CASSCF(8,8)/B3LYP/6-311+G(d,p) geometries.[4] The active orbitals are completely composed of the π orbitals. As shown in

Table S1, the T1 values of st©ructures 7, 9, 12, TS1-3, TS1-15, TS2-7, TS2-11, TS2-12, and TS7-8 are larger than 0.2, indicating the multireference

wavefunction method should be used to calculated their energy. For the structure without multireference character, the CBS-QB3 method is reliable to obtain its

energy. The reaction energy calculated with CBS-QB3 is close to the experimental data, and the maximum deviation is as small as 2.5 kcal/mol [5]. The

energies of structures 4 and 5 without multireference character were calculated using two methods to evaluate the accuracy of CASPT2(8,8)/B3LYP/6-

311+G(d,p). The energy difference between structures 4 and 5 is 0.5 kcal/mol at CASPT2 level, and is 2.7 kcal/mol at CBS-QB3 level. The good agreement

suggests that the accuracy of CASPT2(8,8)/B3LYP/6-311+G(d,p) method is reliable. In this study, the energy calculated with CASPT2(8,8)/B3LYP/6-

311+G(d,p) method is lower than that of CBS-QB3 method, especially for structures 7, 12, TS1-15, TS2-11 and TS2-12. The reason for the difference may be

that the CBS-QB3 method is inadequate to describe multireference character structures with non-negligible static correlation.

Table S1. T1 diagnostic for all structures involved in C4H4+C4H4 reaction.

Species T1 diagnostic Species T1 diagnostic1 0.012717 TS1-2 0.013125

2

2 0.012857 TS1-3 0.0269443 0.014135 TS1-15 0.0523624 0.012621 TS2-7 0.0374075 0.011927 TS2-11 0.0214916 0.019924 TS2-12 0.0210247 0.02247 TS3-4 0.0141548 0.013323 TS4-5 0.0149059 0.030403 TS5-6 0.018831

10 0.010719 TS6-10 0.01628411 0.011562 TS7-8 0.03072712 0.024988 TS8-9 0.01565213 0.011742 TS9-10 0.01345214 0.011513 TS11-14 0.0150815 0.01157 TS12-13 0.01479516 0.012207 TS13-14 0.01635617 0.013814 TS15-16 0.019076

TS16-17 0.01426

Table S2. Comparison of the CASPT2 and CSB-QB3 energies for structures with multireference character, relative to structure 4.Species CASPT2 (kcal/mol) CSB-QB3 (kcal/mol)4 0 05 0.5 2.77 12.6 37.89 -17.3 -14.412 -14.1 5.6TS1-3 50.1 54.4TS1-15 33.6 47.6TS2-7 42.8 50.3TS2-11 35.3 67.3TS2-12 30.5 61.6TS7-8 41.2 45.2

3

Table S3. Total energies, relative energies, zero-point energies, expectation values of S2 operator (projected values are in parentheses), vibrational frequencies, rotational constants, external symmetry number, optical isomers, electronic ground state, Lennard-Jones parameters for all optimized structures at B3LYP/6-311+G(d,p) level in this work.

Species Energies at CSB-QB3

level (hartree):

Relative ZEP

Energy(kcal/mol)

Frequencies (unscaled) (cm-1) RotationalConstants

(GHz)

External symmetry number

Optical isomers

Electronic ground state

/ Å (/kB)/K <S2>

1(C4H4) ZPE:-

154.437535

0 225.7828 320.2508 558.6322655.8077 686.1696 702.6723891.5950 957.0489 1006.75471110.7425 1319.9769 1442.74701662.4000 2198.7280 3137.63603147.3839 3236.8130 3475.3383

1.03341 0.21103 0.17524

1 1 singlet - - 0(0)

2 -308.891679

-10.4 105.1631 152.4093 158.2845303.1535 358.8222 463.7688505.6800 522.4504 543.4000635.5125 646.2438 667.7867726.1634 797.9520 836.9483884.3878 893.9013 978.0753992.1143 1026.6897 1052.18191146.7115 1170.2372 1215.75491245.0648 1278.1299 1295.05121315.7371 1360.8849 1433.85391477.1791 1495.5208 1857.08292216.3611 3036.4831 3058.50353063.2354 3071.2772 3110.94783187.6585 3201.6409 3481.6948

5.13318 1.45817 1.20278

1 1 singlet 5.72 535.6 0(0)

3 -308.799719

47.3 61.3323 90.5447 130.9588 143.9282 240.1154 280.8580

2.84462 1.70205

1 1 singlet 5.72 535.6 0 (0)

4

357.1300 439.8718 458.1023534.2553 557.2818 647.7472670.4716 687.6032 721.3549773.4626 855.1677 870.7181937.1957 957.4081 969.9534995.0597 1026.7291 1077.61011098.9925 1198.6115 1304.12221313.3589 1326.3611 1436.39541444.8108 1662.2935 1674.32351944.5582 2911.9731 3130.13453139.5796 3144.9721 3153.66613218.3253 3243.4537 3334.9714

1.51158

4 -308.896961

-13.7 75.5861 175.5260 181.9733198.7464 260.9819 289.5210471.2759 505.1755 529.1363610.2706 658.6666 683.8960699.9187 812.5069 825.7527882.0258 909.1500 919.36001004.8368 1005.3099 1011.69901013.3328 1152.0513 1216.19901222.2991 1281.6268 1309.93431324.0066 1432.7481 1449.06171593.6035 1602.7481 1646.75181675.8495 3120.8369 3120.96163151.4295 3156.1012 3205.59333220.7048 3237.6395 3244.1694

2.48263 2.16272 1.17137

1 1 singlet 5.72 535.6 0 (0)

5 -308.870782

2.7 68.3767* 173.5324 225.5185290.7636 350.2614 422.5283504.9937 633.4982 673.4758727.8217 751.0818 768.3360819.2610 858.7129 904.6551

3.22752 2.19402 1.75562

1 1 singlet 5.72 535.6 0 (0)

5

924.5309 951.7944 959.94551002.7808 1024.6019 1047.72641049.7694 1077.4129 1138.89511190.4001 1217.3179 1257.41371302.5115 1330.9976 1442.79221446.9448 1519.0198 1585.62261689.9596 3008.9098 3069.77223105.2645 3132.1282 3169.39153173.7357 3205.9031 3214.9324

*Vibration replaced by unsymmetrical hindered

rotor (hrd 5 5 1)

'Vhrd2' 1 0 110.7 -200.7 2.533 104.5 91

'Ihrd1' 1 0 143.5 0.7723 -0.8317 -0.09424 3.214

6 -308.882148

-4.4 75.5225* 130.6743 213.8182305.6661 334.3449 451.8048498.9068 553.1407 583.0754646.8775 767.4961 787.1184862.4541 924.1112 958.1913967.1346 987.2550 1000.36541017.8148 1028.9467 1038.86101106.7795 1141.2530 1201.01201227.3136 1273.5828 1299.74111342.3048 1413.9101 1427.36981449.6031 1521.5608 1587.62761697.3243 2884.6666 3124.57203125.8391 3132.5027 3142.13393146.8008 3151.6868 3221.2875

4.33498 1.67814 1.32846

1 1 singlet 5.72 535.6 0 (0)

*Vibration replaced by unsymmetrical hindered

rotor (hrd 5 5 1)

Vhrd2' 1 0 122.9 -218.4 9.19 53.78 -24.26

Ihrd1' 1 0 110.6 -1.025 0.117 0.2826 -0.08571

6

7 -308.814778

37.8 (CSB-QB3), 12.6

(CASPT2

)

110.3438 192.5842 241.3329300.3962 353.8895 430.1493465.9488 511.2198 567.6048614.9345 668.7368 749.9559769.1585 811.8368 876.2999908.5361 924.2735 942.25211013.3091 1037.7874 1120.57551148.2391 1162.2729 1200.87551225.5505 1267.0294 1296.44361306.9024 1363.2971 1424.61761461.3638 1474.8822 1481.03851808.0840 2971.3817 3012.07543023.0374 3055.3378 3076.00333101.8378 3164.6774 3165.6727

4.81279 1.62256 1.26922

1 1 singlet 5.72 535.6 0 (0)

8 -308.913795

-24.3 83.1390* 165.3566 235.6959236.5357 362.4124 413.5766482.3016 513.3428 603.6294675.5940 714.7295 751.5812799.0114 818.3353 872.4464930.3567 944.3820 956.4659997.7389 1022.2565 1067.86721149.2517 1155.1224 1172.87901254.3574 1300.4312 1303.24871332.4003 1405.3872 1446.58011450.6661 1607.8708 1675.80251815.7662 2973.5847 3049.44623126.2296 3135.8596 3147.74423157.9251 3161.4948 3218.8526

5.16372 1.49812 1.20932

1 1 singlet 5.72 535.6 0 (0)

*Vibration replaced by unsymmetrical hindered

Vhrd2' 1 0 -38.89 167.5 74.83 77.57 226.4

Ihrd1' 1 4.235 100 -0.4104 0.1104 0.06658 5.056

7

rotor (hrd 5 5 1)9 -

308.898061-14.4 (CSB-QB3), -17.3 (CASPT2)

69.1097 139.6263 219.8261235.8852 324.5055 424.4234476.6792 545.6201 586.5996668.1826 727.2005 792.6441812.1994 886.3860 909.7127941.9424 958.3250 970.9352978.0462 1027.3522 1040.99061140.4850 1184.9129 1230.25691261.1775 1303.5336 1332.96551354.1367 1381.1413 1385.04551461.6032 1473.6569 1622.31371660.5337 2974.4804 2980.15133107.4915 3138.6819 3143.46593146.5321 3186.8786 3228.0551

4.84426 1.56482 1.21303

1 1 singlet 5.72 535.6 0 (0)

10 -309.038964

-102.8 46.4866 207.1393 235.1898411.0437 446.5450 448.0568561.0206 634.1140 654.7545708.9466 786.7985 799.7284850.8233 930.9694 933.9291984.3195 1002.4969 1014.09971028.4760 1039.2367 1055.08341110.8731 1182.6099 1205.29181225.4483 1317.8484 1345.33021362.3520 1451.1456 1481.26601526.4317 1614.9775 1640.86611684.4147 3129.4964 3142.78133157.8346 3164.4293 3174.05013182.5087 3190.9371 3222.5256

5.19649 1.53890 1.18729

1 1 singlet 5.72 535.6 0(0)

11 -308.957924

-52.0 103.1688 151.9703 242.2771311.4864 422.9265 486.7374

4.98000 1.49826

1 1 singlet 5.72 535.6 0(0)

8

502.2458 559.2608 584.4442675.4277 685.5874 692.8050758.8604 776.6232 924.8539958.3946 974.8089 983.3073986.7501 998.8767 1064.17611087.4584 1175.7848 1198.50841218.7020 1291.2711 1317.64151349.3579 1391.3031 1432.96291474.2491 1629.7920 1695.06652213.2950 2941.8678 2987.58003077.6933 3154.5476 3163.44513178.5507 3189.2054 3476.3063

1.19326

12 -308.866178

5.6 (CSB-QB3), -14.1 (CASPT2)

84.4742 157.2485 232.1388274.6059 336.6549 419.5217446.2633 545.7769 588.0015646.7568 665.2275 682.9510753.5552 792.5166 858.1038888.2314 914.0119 952.89031028.4472 1042.7841 1126.74911162.8605 1190.0282 1251.28161271.7664 1330.7397 1343.16881354.1173 1375.2555 1408.06251439.7335 1467.5590 1488.98552162.1263 2993.0151 2994.14223010.7896 3032.5532 3055.20973075.5715 3139.9778 3471.7200

4.98039 1.48231 1.20126

1 1 singlet 5.72 535.6 0(0)

13 -308.965813

-56.9 113.3212 157.8745 207.4673310.2793 429.9912 472.0656514.4204 547.3828 569.8891631.6834 685.1824 703.6943744.3275 765.4949 886.8606

5.02815 1.46406 1.16669

1 1 singlet 5.72 535.60（0）

9

916.4628 973.7411 990.95411007.0596 1040.0986 1072.50461163.8343 1185.6576 1200.94011269.2645 1326.6889 1359.36951380.8569 1423.4056 1470.29261480.4012 1608.4245 1679.64952181.5927 2968.1492 2988.88153061.0127 3082.1895 3155.70313173.0365 3183.6620 3475.7139

14 -307.812321

-64.8 141.4807 160.7152 366.9608408.9963 472.8958 538.7748549.9694 636.3435 646.8478697.0765 702.6910 773.8646775.2449 854.1320 936.2732987.1415 1004.9989 1014.45471047.9319 1100.3916 1183.49481199.9245 1221.9675 1312.65211352.3497 1472.0489 1520.20441608.6993 1639.2966 2201.87293165.7823 3174.6002 3185.15463192.8923 3196.9039 3476.4267

5.69713 1.53069 1.20653

1 1 singlet 5.72 535.60 （0）

15 -308.921639

-29.2 97.5376 121.7530 179.1318209.1955 246.9207 371.1922464.2271 501.4685 566.1463665.9120 675.1088 677.3842694.9459 793.2582 845.3028905.2297 944.8693 946.67041007.1582 1015.6433 1022.02701065.2504 1109.5965 1166.52341219.2316 1228.0248 1302.23501317.6235 1326.3743 1444.4187

2.55255 2.04972 1.22610

1 1 singlet 5.72 535.60(0）

10

1475.2175 1631.1097 1700.27992206.8952 3031.7519 3035.84513082.9659 3130.3578 3142.15783182.9030 3226.6233 3477.3941

16 -308.909606

-21.7 122.9525 166.4991 255.9034283.0618 308.7040 449.7819514.6886 573.0936 589.7010673.9246 716.3311 786.5352800.8977 866.1947 877.4157893.1481 896.4551 980.1786998.2985 998.8650 1124.28351125.5524 1183.7322 1184.19131276.3063 1279.6136 1298.43091298.6055 1417.0379 1427.36761476.9933 1478.6022 1998.17391999.7624 3051.0166 3051.88333095.4259 3096.1829 3132.65783132.7970 3135.9031 3137.6262

3.31480 2.29201 1.46774

1 1 singlet 5.72 535.60(0）

17 -308.934957

-37.6 156.5649 182.2575 255.3251336.5804 450.0893 521.6144563.0209 590.1849 665.6383672.6213 675.7580 727.9957793.7994 811.3545 847.5058849.6429 922.6852 945.4524970.2870 1007.8781 1021.86801044.1590 1160.2693 1169.84811219.8910 1240.4367 1253.22861299.1251 1302.6332 1324.32611335.1133 1374.0467 1474.19651566.0410 2981.3820 2981.5360

4.76123 2.05035 1.45843

1 1 singlet 5.72 535.60(0）

11

2994.8168 2995.9753 3226.78463228.9426 3229.9817 3232.5329

TS1-2 -308.832057

27.0 -482.7464 68.2652 109.9719152.3773 238.1165 263.5855334.6786 399.2003 475.5254525.9503 565.3953 589.1548594.4321 625.4074 684.6974712.8607 765.2437 797.9500863.7339 905.9898 946.64911025.1422 1050.5228 1139.05691159.6593 1164.8409 1215.42631250.6462 1403.9515 1423.01431495.3324 1511.8622 2032.05542163.4367 3103.6049 3111.46543162.4388 3179.4611 3188.04533196.7093 3418.0985 3475.7782

3.45395 1.55256 1.24816

1 1 singlet - -0（0）

TS1-3 -308.788442

54.4 (CSB-QB3), 55.1 (CASPT2)

-379.9029 67.4932 113.2631141.3298 166.7275 211.8515273.2032 355.2751 360.6987405.4053 514.5789 539.6914561.9793 648.5703 705.6941729.1392 793.1567 810.9208875.6368 927.5144 931.0161973.5025 997.9065 1013.02541084.0754 1132.0353 1315.07671321.4452 1423.9596 1432.08541527.0683 1668.2941 1672.76671946.5996 3071.6948 3132.34073148.1949 3150.5828 3165.70313230.3660 3243.4984 3438.2822

2.66254 1.71997 1.60660

1 1 singlet - -0 （0）

12

TS1-15 -308.799239

47.6 (CSB-QB3), 33.6(CASPT2)

-345.8421 64.9007 119.2135166.5430 211.0692 263.5352309.4083 353.9236 411.5156484.7057 493.0892 546.7283590.4664 662.5270 674.7575679.5400 715.2272 749.1974772.6803 906.4958 933.8434944.0214 1017.3603 1025.31181134.1032 1174.8091 1254.65231336.2010 1358.1853 1443.43741452.5884 1641.2796 1665.04672208.6144 2987.6192 3143.35203143.5166 3155.6783 3227.95963272.5044 3288.0458 3477.7913

2.79046 1.53058 1.37380

1 1 singlet - -0（0）

TS2-7 -308.794883

50.3 (CSB-QB3),

42.8(CASPT

2)

-828.0268 96.0838 131.4225268.6363 333.6285 380.1937428.9115 465.3890 496.9572534.5741 589.7107 635.8586707.0321 748.2084 758.0077778.4360 852.5713 876.4708930.3093 948.6935 1029.28001124.0934 1135.0788 1166.48751195.1842 1253.9200 1300.88441310.3823 1332.0347 1393.05751471.9587 1481.6683 1750.59481858.5460 2403.2216 3014.25813046.3303 3070.7300 3092.69893157.4870 3163.4119 3281.7253

5.18325 1.45810 1.20001

1 1 singlet - -0（0）

TS2-11 -308.76775 67.3 -1926.9966 95.4406 151.3476165.7867 283.1496 424.5351463.2455 500.1049 538.1838

5.27475 1.47219 1.21463

1 1 singlet - -0（0）

13

570.1359 626.7611 679.9996683.8272 690.7430 798.4093807.3202 894.6201 918.6749944.0560 992.2763 995.74041039.3115 1061.1844 1145.83011152.5023 1254.2083 1262.58681290.9426 1343.3476 1360.1561 1432.2867 1491.4126 1506.49261582.2490 2211.8142 2991.61523019.1290 3062.0604 3134.51613154.3188 3164.7954 3475.8900

TS2-12 -308.776922

61.6 -1935.6474 112.7747 151.5958202.5975 321.8246 432.1313483.6853 514.7977 535.7000537.4151 581.6371 649.8309695.1288 718.9707 782.1742809.8241 863.4109 912.3391956.8788 969.6103 1045.61551083.9590 1108.0427 1170.84461200.3734 1237.0252 1298.73201302.3303 1332.0987 1418.66431477.3120 1500.1579 1519.44161589.9660 2168.2045 3023.47863025.6369 3067.0385 3086.69193163.3632 3164.3581 3476.5257

4.82186 1.50835 1.24004

1 1 singlet - -0（0）

TS3-4 -308.798665

47.9 -159.2822 61.1439 116.1136146.1620 197.8170 266.3351356.4771 449.4491 505.0173527.1025 566.1254 603.6797648.3683 719.9489 754.4066772.6887 896.0838 925.8916

2.76184 1.79658 1.46034

1 1 singlet - -0（0）

14

941.6610 950.2826 971.14871006.1812 1021.0107 1084.84561127.7068 1213.7486 1306.53151317.0230 1326.2167 1437.37671446.4483 1659.9669 1676.11561888.2126 2897.6279 3129.60753138.3583 3146.8346 3155.04163216.9376 3240.5383 3336.0918

TS4-5 -308.842082

20.7 -506.3780 140.4321 173.0550264.6296 279.9130 344.7572455.4032 516.2392 605.9967647.7665 675.4786 748.5709803.6082 823.7796 852.7616885.2105 899.3896 931.1278977.4809 992.2547 1008.43701046.0112 1111.5996 1136.75021177.1947 1246.9430 1312.09721315.7134 1371.6526 1387.81181465.4988 1474.5192 1590.22601645.2587 3090.7347 3122.16273135.3350 3170.5503 3175.02553197.7432 3200.5106 3220.9934

3.12229 2.18172 1.55308

1 1 singlet - -0（0）

TS5-6 -308.785212

56.4 -836.1902 72.8510* 167.3085224.5211 256.7979 359.7497411.2901 443.8227 553.6472649.3742 666.8064 703.3177774.7049 808.6837 834.6084915.6076 936.5087 964.4684968.7463 981.5562 1021.67001032.1228 1070.2929 1107.24521175.1612 1236.6289 1287.4067

3.10568 2.12671 1.56759

1 1 singlet - -0（0）

15

1321.9878 1333.4214 1379.40531442.5122 1450.2152 1518.25891681.5710 1712.3759 3079.31053128.3477 3138.7443 3172.86073182.2097 3212.2530 3224.8416

*Vibration replaced by unsymmetrical hindered

rotor (hrd 5 5 1)

Vhrd2' 1 0 411.2 -198.4 1.563 78.2 44

Ihrd1' 1 0 172.3 15.37 -7.401 -21.02 -16.52

TS6-10 -308.832238

26.9 -775.5121 96.0004* 205.0033274.7956 407.7185 421.6629463.7004 524.9748 558.3222651.9394 673.6561 688.3544743.0622 798.0316 861.4104862.8267 891.1690 959.4017993.0241 1006.6871 1028.39091048.7212 1067.6253 1076.88801136.1069 1232.8698 1302.69111324.2584 1331.5922 1372.50361444.7007 1525.6625 1569.04861676.5663 2002.5262 3134.62573143.8331 3193.7766 3196.29233221.1574 3222.7900 3224.2880

4.67138 1 1 singlet - -0（0）

*Vibration replaced by unsymmetrical hindered

rotor (hrd 5 5 1)

Vhrd2' 1 0 341.2123 -214.2445 4.1233 65.413 -3.225

Ihrd1' 1 1.001 130.2 2.152 2.325 0.8025 6.824

TS7-8 -308.803042

45.2 (CSB-QB3),

41.2

-1319.9102 159.3776 226.1325287.2008 325.8789 351.3892511.0204 527.9528 587.8770646.3540 711.7669 724.8790

4.67138 1.74657 1.33378

1 1 singlet - -0（0）

16

(CASPT2)

769.3171 815.8359 833.4065873.7257 934.1434 947.7511974.3754 1013.6892 1024.43631117.4607 1140.2559 1164.04971238.4570 1249.4534 1273.00021332.1130 1351.6828 1405.71851415.8631 1446.4621 1473.08051736.4244 1818.0786 3035.34453042.5778 3085.1963 3099.58063114.3487 3154.1799 3172.5667

TS8-9 -308.86845 4.2 -1008.5683 85.4209* 177.5319232.0422 319.2293 408.9031454.0299 551.9872 600.2813635.7983 713.0789 764.6497787.7556 873.2185 920.0774930.5185 956.2101 993.61011027.2075 1047.7528 1060.44241077.5172 1145.4763 1191.58681214.7083 1306.8007 1324.91651343.9643 1372.6287 1431.98211457.7754 1487.8325 1591.65321681.2007 2137.7253 3089.04793121.9833 3136.4096 3143.11633144.8210 3192.4030 3221.0460

5.05495 1.54600 1.20175

1 1 singlet - -0（0）

*Vibration replaced by unsymmetrical hindered

rotor (hrd 5 5 1)

Vhrd2' 1 0 242.624 -101.5364 4.425 6.4162 -22.467

Ihrd1' 1 -0.8112 103.8 2.572 -0.235 2.68 -0.668 -0.8112

TS9-10 -308.89462 -12.3 -820.7420 59.3854 169.3269241.0798 286.2652 420.3642444.8110 558.9290 609.7249

5.06448 1.54805 1.19256

1 1 singlet - -0（0）

17

630.6105 672.8870 758.4387790.3751 850.1185 933.1442952.3527 954.3446 994.63431006.4990 1031.9184 1041.25281069.8097 1193.8124 1201.24361225.4362 1257.6643 1330.51091365.9911 1402.0604 1450.01791480.1283 1511.4461 1635.99811680.5525 2291.3881 3112.57153118.6378 3140.3654 3146.30323158.2063 3186.2130 3224.7850

TS11-14 -308.801091

46.4 -2662.7520 96.2982 151.8648259.7689 396.9380 416.7377468.9992 498.8413 549.4042617.7489 652.8536 664.4173686.6888 711.6208 740.0953746.7386 782.1782 868.3741942.5829 969.0346 982.27511013.2193 1048.7540 1110.55691142.8818 1173.1234 1208.63781230.1841 1273.6151 1342.56871428.2102 1487.5237 1542.21011617.8360 1753.3690 2226.95963160.8304 3164.9464 3204.49623208.1505 3220.0601 3475.3193

5.18586 1.48888 1.19250

1 1 singlet - -0（0）

TS12-13 -308.848486

16.7 -1085.7050 114.1330 158.3895206.6242 303.3500 431.1784452.3219 512.3471 552.0258585.1692 664.3832 683.4220687.9340 768.4392 811.1330878.6890 919.1077 958.2279

5.03360 1.46901 1.17850

1 1 singlet - -0（0）

18

1001.3487 1028.5885 1063.59131159.3224 1173.3383 1228.52071258.0169 1325.2611 1344.49271363.0102 1382.6089 1439.58711470.7707 1477.7199 2135.8682 2135.8682 2184.1750 2986.63333013.3686 3074.0969 3082.39953104.5109 3158.2407 3473.9083

TS13-14 -308.813044

38.9 -2209.4956 111.5119 155.4767223.0372 379.2206 428.4295512.0775 535.0759 545.2745551.2107 572.3956 647.8356706.1188 735.2116 761.3845773.3572 885.0608 936.7625953.3967 959.9973 1007.59941040.7248 1064.2107 1146.76791157.7261 1206.5764 1246.29301310.5568 1366.2299 1404.59441412.5082 1490.6743 1602.90801633.9530 2020.6259 2168.06913162.4495 3168.7654 3173.44753206.1000 3219.6718 3476.8845

5.04074 1.48558 1.18654

1 1 singlet - -0（0）

TS15-16 -308.860865

8.9 -244.1052 206.0897 213.5535310.1858 397.6074 447.7630504.2885 514.5121 573.6336634.9765 714.0069 751.4473769.4488 782.6592 834.2682947.8311 956.5697 988.94261006.4926 1017.8720 1084.51921090.3874 1126.6543 1170.41811183.1460 1220.8946 1236.1620

4.15258 2.12711 1.51550

1 1 singlet - -0（0）

19

1249.3634 1330.7856 1392.78901468.2983 1509.8602 1661.40491784.0177 3015.6150 3043.98253065.5216 3072.5174 3136.86063155.3632 3179.4486 3254.2522

TS16-17 -308.862633

7.8 -701.1400 179.7121 267.3849299.1661 326.2953 328.3656509.7065 511.5185 631.3275652.6991 669.0731 721.9031747.6635 793.0767 868.5591885.8608 907.9393 929.6115962.5417 1008.4209 1056.63311076.4419 1095.4149 1143.18661198.6631 1254.3294 1274.05891291.6769 1380.0488 1384.01261416.7949 1423.0730 1799.44191817.8207 2974.9964 2975.74893046.9760 3047.5342 3148.73053149.4322 3151.0972 3152.8438

4.19907 2.04738 1.42162

1 1 singlet - -0（0）

Table S4. Cartesian coordinates of optimized structures at B3LYP/6-311+G(d,p) level.Species Geometry(Ǻ)1 C 1.66029700 -0.37191800 0.00004900

C 0.63581100 0.48905400 -0.00017100 C -0.73544000 0.11071100 -0.00048300 C -1.90738400 -0.17224400 0.00037500 H 1.50202400 -1.44384100 -0.00029700 H 2.68329400 -0.01580800 0.00095800 H 0.83255300 1.55844100 0.00061200 H -2.93757700 -0.43240700 0.00010600

20

2 C 1.73496200 1.06756900 0.14247000 C 0.17346700 1.15081000 0.21385400 C 2.21131000 -0.33571700 -0.25013000 C 1.36459900 -1.29480000 0.09132600 C -0.59301100 -0.09758200 -0.38684900 C -2.03514000 0.01196500 -0.17549300 C -3.22795300 0.10276700 0.01044800 H 2.11232000 1.74923600 -0.63045500 H -0.15159300 1.24971300 1.25385900 H -0.16656000 2.04909800 -0.31269200 H -0.39606100 -0.14325100 -1.46396100 H -4.27963500 0.17906600 0.16805800 H 2.16445400 1.41253500 1.09046900 C 0.05950200 -1.30348600 0.30938200 H -0.47108700 -1.85298200 1.08058400 H 3.06174800 -0.45256400 -0.91590700

3 C -1.84437600 -1.54498800 -0.03553100 C 2.33171100 -0.53586700 -0.86883900 C -1.57404200 -0.36661900 -0.60138900 C -0.64990000 0.69470000 -0.09283000 C 1.88978200 -0.43277300 0.38764000 C 0.64247500 0.16667400 0.74912800 C -0.30225500 0.61017100 1.46002300 H -2.54529400 -2.23439800 -0.49148900 H 3.28880000 -0.99267500 -1.08698100 H 1.74837800 -0.16344100 -1.70252400 H 2.48257700 -0.80684200 1.21831700 H -0.85315500 0.85192400 2.34726300 H -1.37716900 -1.86300600 0.89031100 C -0.42943900 1.95799700 -0.67367800 H -1.05536300 2.01921300 -1.58926100

21

H -2.07250900 -0.10654200 -1.532790004 C 1.82536300 -1.70835800 0.21997100

C -1.82344600 -1.71006700 -0.21985200 C 1.87829600 -0.40306900 -0.10635700 C 0.79939600 0.53308700 -0.09046200 C -1.87808200 -0.40476300 0.10617900 C -0.80017200 0.53248800 0.09034400 C -0.75187300 1.88391700 0.10268700 H 2.71622400 -2.32372000 0.19409500 H -2.71350700 -2.32660000 -0.19401800 H -0.90560500 -2.18309300 -0.54405500 H -2.84179600 0.02525200 0.37546500 H -1.50421400 2.65757800 0.17735300 H 0.90823300 -2.18251400 0.54451200 C 0.75007600 1.88448800 -0.10258800 H 1.50187600 2.65871400 -0.17693500 H 2.84143700 0.02805000 -0.37594900

5 C 2.36170800 -0.03651400 -0.68510100 C -0.48971300 1.43072600 0.72228900 C 1.60987200 -0.11169400 0.41101900 C 0.12012100 -0.01948900 0.45791600 C -1.23212500 1.26627600 -0.60555300 C -0.77956300 -0.00067100 -0.76616700 C -1.25906500 -1.37520000 -0.46323700 H 3.44274500 -0.10284700 -0.63194300 H -1.20675300 1.47608500 1.55231500 H 0.26163000 2.21489600 0.84764900 H -2.11452400 1.76903100 -0.98513200 H -1.97918400 -2.04573900 -0.91494200 H 1.92071100 0.09219600 -1.66793100 C -0.62763800 -1.34480300 0.73451700

22

H -0.64006800 -2.01625800 1.58633500 H 2.09385100 -0.23915400 1.37955000

6 C -2.62643100 0.34640400 -0.59430300 C 0.07855600 1.13683800 0.35582900 C -1.90070700 -0.45657600 0.17769500 C -0.45703200 -0.23437800 0.60138100 C 1.34702200 1.33797900 -0.08348800 C 2.28738400 0.25418400 -0.17433300 C 1.69152600 -1.03644500 -0.37848600 H -3.64973900 0.09507600 -0.84848600 H -0.55170900 1.97121200 0.65160100 H -0.45129200 -0.36937900 1.70284000 H 1.71131500 2.35619200 -0.19932200 H 2.31726700 -1.85379900 -0.72947500 H -2.23391100 1.27036200 -1.00393500 C 0.43534800 -1.30822500 0.05726300 H 0.06519000 -2.32928900 0.10835100 H -2.34111900 -1.37905300 0.54908000

7 C -1.47958700 -1.13460400 0.42142200 C -0.04025800 -1.06617700 -0.19439300 C -2.22230700 0.01874000 -0.24993100 C -1.55412200 1.13664300 -0.08025100 C 0.61639500 0.29408200 -0.05914200 C 2.00162400 0.44909600 0.03487500 C 2.85975400 -0.64922200 -0.01389400 H -1.94626000 -2.09795000 0.20514100 H 0.63971000 -1.79338800 0.25781000 H -0.10272700 -1.33565500 -1.25555500 H 2.34900900 1.48719100 0.11547000 H 3.86928800 -0.32535900 -0.31993000 H -1.43368900 -1.01956000 1.50652400

23

C -0.26745700 1.43522200 0.12505400 H 0.11402200 2.33176400 0.60220600 H -2.97361000 -0.14972300 -1.01411300

8 C 1.57873500 1.19937300 0.17274000 C 0.07594000 1.00880000 -0.04782600 C 2.31383200 -0.06564100 -0.23790700 C 1.62007000 -1.16074900 0.03054000 C -0.53360500 -0.19776900 -0.09203300 C -1.97451600 -0.40415300 -0.31965600 C -2.96342300 0.38139700 0.11503100 H 1.93839100 2.01165700 -0.46797300 H -2.77316900 1.26286700 0.71830900 H -0.51398300 1.91334500 -0.16180900 H -2.22772500 -1.30480700 -0.87576500 H -3.99889000 0.15655800 -0.11273900 H 1.74906800 1.54610700 1.20375700 C 0.33718200 -1.34406400 0.31321300 H -0.04890400 -2.07393100 1.01859900 H 3.14992900 -0.01496200 -0.92699100

9 C -1.35993000 -1.28975200 -0.11377800 C -0.02782300 -1.07983500 -0.18780200 C -2.25640700 -0.15137100 0.22851200 C -1.68407600 1.22491900 0.17706300 C 0.51559100 0.25577200 -0.12691400 C 1.94904300 0.49878000 -0.00663900 C 2.90084200 -0.41848300 0.21998300 H -1.78054300 -2.26702800 -0.33553900 H 2.67751100 -1.46828300 0.37149800 H 0.64673500 -1.90767800 -0.37100500 H 2.24696700 1.53884500 -0.11628700 H 3.94571500 -0.13543200 0.26608800

24

H -2.68330600 -0.28763100 1.23480100 C -0.36194500 1.35225100 -0.22741900 H 0.05834000 2.33696600 -0.42671500 H -3.16318600 -0.16345500 -0.40088700

10 C 2.97316700 0.33529000 0.00078400 C 0.00915000 1.09043100 -0.00061400 C 1.95349100 -0.52898700 -0.00043800 C 0.51416400 -0.22070900 -0.00062300 C -1.35985000 1.32776000 0.00000100 C -2.26230800 0.26170200 0.00049100 C -1.77913400 -1.04427100 0.00012700 H 3.99774100 -0.01657400 0.00087600 H -3.32986000 0.45037500 0.00076200 H 0.69169400 1.93227300 -0.00138800 H -1.72768700 2.34790600 0.00001200 H -2.46946100 -1.88050700 0.00058500 H 2.83327400 1.41051500 0.00172900 C -0.40628500 -1.27987700 -0.00002800 H -0.03662700 -2.30032400 0.00030900 H 2.18655500 -1.59169400 -0.00108200

11 C 1.60919700 -1.15526600 -0.00199200 C 0.11263600 -1.24621800 -0.17138200 C 2.22262600 0.03691300 -0.00343400 C 1.44608400 1.27041400 -0.14955300 C -0.59790100 -0.00812600 0.42611000 C -2.02211600 0.00668700 0.09662600 C -3.19244800 0.01120100 -0.18064500 H 2.18111600 -2.07552000 0.05580100 H -0.12516200 -1.31647500 -1.24304400 H -0.28463900 -2.15094800 0.29400500 H -0.51500200 -0.07773300 1.52404700

25

H -4.22677700 0.01697200 -0.42348700 H 1.96857800 2.19161300 -0.38506900 C 0.11663100 1.27227600 0.01457300 H -0.46904600 2.17964200 -0.07471200 H 3.30268100 0.10516300 0.07064500

12 C 1.59508000 -1.05170600 -0.34046900 C 0.15337300 -1.21033300 0.13441400 C 2.17547400 0.23329100 0.27711800 C 1.26866800 1.40829500 0.23758300 C -0.63410700 0.05631500 -0.10518600 C -2.03838100 -0.00371700 0.02793700 C -3.24176700 -0.07793800 0.11770500 H 2.18918400 -1.92999000 -0.07433500 H -0.35207900 -2.02970800 -0.38711200 H 0.11978300 -1.47035900 1.20194000 H 2.48282300 0.08425000 1.32248300 H -4.30064100 -0.13303800 0.19096300 H 1.60598500 -0.96489300 -1.43176400 C 0.00909800 1.27303200 -0.34210900 H -0.57502100 2.13863800 -0.64171100 H 3.10534600 0.54166700 -0.22242200

13 C 1.51395400 -1.18554700 -0.27273200 C 0.09492900 -1.20472000 0.31254900 C 2.21058600 0.12525200 -0.00976500 C 1.50089100 1.26164800 0.08330900 C -0.65103000 0.09477000 0.03938600 C -2.06754700 0.05838200 -0.03392000 C -3.27135700 -0.02037200 -0.08597800 H 2.09216500 -2.02125200 0.13099200 H -0.46880700 -2.05270500 -0.08132300 H 0.14208100 -1.33999800 1.40283400

26

H 1.99936400 2.21560700 0.21828500 H -4.33116300 -0.07527000 -0.13520900 H 1.47058700 -1.34295500 -1.36169100 C 0.04881400 1.25087400 -0.03862400 H -0.47418300 2.19055000 -0.17594700 H 3.29451700 0.14430300 0.03672400

14 C 3.22699800 0.00000800 0.00001800 C -0.11926700 -1.21090600 -0.00000400 C 2.02199000 -0.00002900 -0.00001400 C 0.59379600 -0.00001500 -0.00000800 C -1.50998000 -1.20653600 0.00000200 C -2.20962800 0.00001700 0.00000500 C -1.50995200 1.20655500 0.00000200 H -3.29366500 0.00003000 0.00001000 H 0.42691900 -2.14641400 -0.00000600 H -2.04902400 -2.14715300 0.00000500 H -2.04897400 2.14718400 0.00000500 H 4.28947200 0.00004600 0.00000700 C -0.11923900 1.21089200 -0.00000400 H 0.42696900 2.14638800 -0.00000700

15 C -1.20350800 -1.59606700 0.15809400 C 2.18391800 1.30627700 0.21683900 C 0.18555500 -1.82651500 -0.39272200 C 0.65269000 -0.60704600 -0.06438300 C -1.93875200 1.94034300 -0.41079000 C -1.36145600 0.98581700 0.04116000 C -0.67007300 -0.16893700 0.58936500 H -1.51141100 -2.23262300 0.99329600 H 1.42945700 1.90633400 0.71349500 H 3.15835900 1.75844900 0.07654700 H -2.44727000 2.78135500 -0.81430400

27

H -0.59139000 -0.07193600 1.67749900 H -2.00954500 -1.55907600 -0.57877100 C 1.92293300 0.06659800 -0.21639100 H 2.70178400 -0.50084200 -0.72180900 H 0.64216800 -2.68447700 -0.87298100

16 C 1.94352100 0.00007400 -0.36349300 C -1.94345300 -0.00006000 0.36359300 C 1.26877500 1.24258400 0.24414400 C -0.00008500 1.45455100 -0.00003900 C -1.26879700 -1.24255800 -0.24423600 C 0.00005700 -1.45459300 -0.00005300 C 1.26889200 -1.24250100 0.24420400 H 3.01130700 0.00011200 -0.13718800 H -1.83752200 -0.00008900 1.45108800 H -3.01130100 -0.00015000 0.13761200 H -1.80662800 -1.81360500 -0.99679800 H 1.80671800 -1.81360200 0.99671600 H 1.83794400 0.00003900 -1.45102600 C -1.26894800 1.24249500 -0.24419100 H -1.80681400 1.81361300 -0.99668100 H 1.80652700 1.81372700 0.99670000

17 C -2.19476700 0.00000000 0.00015500 C 2.19476700 0.00000000 0.00002800 C -1.31675100 1.20408200 0.00008000 C 0.00000000 0.75263700 -0.00003100 C 1.31675100 -1.20408200 -0.00017700 C 0.00000000 -0.75263700 -0.00003400 C -1.31675100 -1.20408200 0.00007100 H -2.87234900 0.00000900 -0.87028600 H 2.87307000 0.00000600 -0.86983700 H 2.87210900 -0.00000500 0.87066100

28

H 1.67671900 -2.22209800 0.00058400 H -1.67671900 -2.22209800 -0.00069600 H -2.87283100 -0.00001100 0.87021300 C 1.31675100 1.20408200 -0.00017300 H 1.67672000 2.22209800 0.00057000 H -1.67671700 2.22209900 -0.00071600

TS1-2 C 1.49299100 -0.93378700 -0.73895900 C 0.12320900 -1.39289200 0.50972400 C 2.16319700 0.17908000 -0.17992600 C 1.37163800 1.28662100 -0.04008200 C -0.78849600 -0.35186000 0.83264400 C -1.94012500 -0.10789100 0.05565100 C -2.91783900 0.11529200 -0.62131800 H 2.05026300 -1.86255900 -0.83780700 H -0.28941100 -2.18701600 -0.10648700 H 0.71758300 -1.76295400 1.33833500 H -0.75095900 0.10163600 1.81466300 H -3.78652600 0.29506100 -1.20568000 H 0.83607700 -0.73796300 -1.57979300 C 0.27707000 1.80591000 0.18670600 H -0.53793100 2.49252800 0.14894200 H 3.07104000 0.05842700 0.40117100

TS1-3 C -1.81953600 -1.47443700 -0.23416700 C 2.18673400 -0.42796300 -1.00016100 C -1.60350900 -0.21559200 -0.62967900 C -0.59915600 0.75226000 -0.16884800 C 1.79377900 -0.53613200 0.26958200 C 0.58549000 0.04970100 0.80393500 C -0.12364300 0.27309000 1.80768600 H -2.60709300 -2.06259000 -0.69001800 H 3.11186600 -0.88123500 -1.33346000

29

H 1.60123700 0.12048800 -1.72805100 H 2.39258800 -1.07954700 0.99375200 H -0.83722500 0.62133100 2.51796000 H -1.23815500 -1.95083100 0.54553900 C -0.32630800 2.01717900 -0.43579200 H -0.75019100 2.40784900 -1.36758600 H -2.23613900 0.19589300 -1.41346900

TS1-15 C 0.94621700 1.29534900 1.30475100 C -2.27360900 -1.17786000 0.46304400 C -0.23698100 1.42351400 -1.24632800 C -0.59933800 0.50639700 -0.40542900 C 2.41932500 -1.29298100 -0.66358700 C 1.55970200 -0.67362600 -0.09485100 C 0.53044400 0.05798800 0.64931200 H 0.82313500 2.23724600 0.79177900 H -1.58846500 -1.68979500 1.12725300 H -3.28716000 -1.56055600 0.42739000 H 3.17680600 -1.82681500 -1.18282700 H 0.15997400 -0.63597900 1.41648500 H 1.34094300 1.27692600 2.31462000 C -1.92147400 -0.13826200 -0.30111000 H -2.67187500 0.29892700 -0.95293800 H -0.49906700 1.89692600 -2.17657900

TS2-7 C 1.68022100 -1.00637600 -0.41923200 C 0.26522000 -1.17698600 0.21408500 C 2.24332000 0.27029200 0.20533900 C 1.41485800 1.28772800 0.07439100 C -0.58668600 0.08783200 0.07301500 C -2.01299600 -0.01022300 0.11714600 C -3.22239900 -0.13005600 -0.24340600 H 2.29767000 -1.88065400 -0.19911000

30

H -0.26530600 -1.99989400 -0.27327100 H 0.38434500 -1.45336000 1.26867400 H -1.70519200 0.14493500 1.24459000 H -4.17622800 -0.16253800 0.25529500 H 1.59541600 -0.92005700 -1.50526200 C 0.08766800 1.32803000 -0.18582900 H -0.43155300 2.13427200 -0.69270900 H 3.08561800 0.23584900 0.88874100

TS2-11 C -1.65806900 1.00711700 -0.22939600 C -0.13912100 1.23564500 -0.11427000 C -2.22396500 -0.14722600 0.33222500 C -1.48014600 -1.29968800 -0.12645500 C 0.59103200 -0.04125900 0.40012500 C 2.02651900 -0.00200000 0.15342500 C 3.20894600 0.01505800 -0.06718600 H -2.25007700 1.86286200 -0.54296100 H 0.28683500 1.56265600 -1.06980200 H 0.03708700 2.04297300 0.60282400 H 0.41682300 -0.09692700 1.48315700 H 4.25428400 0.03134000 -0.25711500 H -1.22097000 -0.21896900 -1.00931300 C -0.12234800 -1.26215700 -0.22053400 H 0.46032000 -1.99138200 -0.77343400 H -3.20138800 -0.22549300 0.79903800

TS2-12 C 1.73705400 1.00422100 0.23018500 C 0.20842300 1.25118400 0.13232700 C 2.06647500 -0.30441700 -0.48986700 C 1.26008200 -1.36378800 -0.18574800 C -0.60501700 -0.08548000 0.08549300 C -2.00715500 0.01279600 -0.08425700 C -3.20194000 0.10819300 -0.24452600

31

H 2.29513300 1.84958700 -0.17844500 H -0.12020800 1.81362500 1.01030900 H -0.04370800 1.85293900 -0.74708500 H 0.48553300 -0.44776700 -0.93739900 H -4.25203500 0.18227500 -0.38574300 H 2.01491600 0.89420200 1.28378500 C 0.06303800 -1.25271900 0.55671200 H -0.33278500 -2.01932200 1.21470500 H 2.82739500 -0.34547700 -1.26203100

TS3-4 C 1.39717700 1.81658000 0.40815200 C -2.38234400 0.55310900 -0.77720300 C 1.41141500 0.79204600 -0.44592600 C 0.71187700 -0.52193000 -0.29160900 C -1.94295200 0.01260000 0.36423500 C -0.61722000 -0.50817900 0.52870800 C 0.32687800 -1.04795500 1.19229100 H 1.95673200 2.72211000 0.20439200 H -3.39423200 0.92880800 -0.86488700 H -1.73975700 0.63421700 -1.64601300 H -2.59562500 -0.06343600 1.22929100 H 0.86764800 -1.46611900 2.01793300 H 0.83464800 1.78711800 1.33545900 C 1.09609900 -1.73885600 -0.89795200 H 2.07444700 -1.56427500 -1.39728700 H 1.99056300 0.87708800 -1.36305700

TS4-5 C 2.40675200 0.02952500 -0.59897800 C -0.14559800 1.67168100 0.75005300 C 1.59034000 -0.62779200 0.24172000 C 0.16136800 -0.43078800 0.36311200 C -1.07318700 1.46515000 -0.33561000 C -0.87615200 0.15370300 -0.63813600

32

C -1.65922700 -1.03541200 -0.48594900 H 3.46866600 -0.18219500 -0.63008900 H -0.49719900 2.21692500 1.62638600 H 0.92228900 1.72899100 0.58464300 H -1.96913900 2.04406600 -0.52912400 H -2.65590200 -1.31420800 -0.80554700 H 2.03202700 0.77307100 -1.29466800 C -0.81042600 -1.48612000 0.52592900 H -0.87592500 -2.32345800 1.21243400 H 2.01196500 -1.38287700 0.90311800

TS5-6 C 2.41879600 0.16933100 -0.64114900 C -0.53827700 1.67981100 0.88458300 C 1.67709900 -0.41521400 0.30066200 C 0.20459200 -0.34434800 0.36963000 C -1.21775100 1.39748400 -0.32702000 C -0.79560200 0.13468000 -0.69944500 C -1.51885100 -1.13311100 -0.50742400 H 3.49738000 0.06362400 -0.65202300 H -0.14913700 0.43267800 1.34000000 H 0.45697000 2.13268500 0.89672100 H -2.10770900 1.91018500 -0.67460500 H -2.44081600 -1.53591200 -0.91073900 H 1.96486900 0.75650300 -1.43223900 C -0.68361600 -1.54621100 0.48886700 H -0.65711300 -2.40825400 1.14250100 H 2.15721900 -1.00604300 1.07816600

TS6-10 C -2.78798300 0.24366900 0.15497600 C 0.04826800 1.14910700 -0.49949700 C -1.76517200 -0.61279200 0.11612100 C -0.32995100 -0.23201000 0.01926100 C 1.28486000 1.42483800 -0.05030100

33

C 1.62981000 0.28256900 0.80351900 C 1.87669400 -0.93580700 0.02176600 H -3.81109600 -0.10977800 0.20986400 H -0.59326300 1.76471100 -1.11567900 H 0.11619400 -0.09001300 1.14117600 H 1.93470200 2.26140900 -0.26664300 H 2.84692100 -1.38248100 -0.14566800 H -2.64032400 1.31786800 0.13877700 C 0.66313800 -1.30138100 -0.42465300 H 0.39190300 -2.19015200 -0.97917100 H -1.96301400 -1.68072900 0.17019200

TS7-8 C -1.31281600 -1.24676700 0.33379400 C 0.10567100 -0.94023000 -0.26606000 C -2.20177800 -0.12087900 -0.16956900 C -1.63016000 1.04490000 0.05577800 C 0.56216000 0.44531600 -0.20773900 C 1.97549300 0.52865300 -0.13182100 C 2.61276100 -0.63089400 0.24382400 H -1.68120900 -2.21733200 -0.00316900 H 1.18696100 -1.36021900 0.28394200 H 0.26914400 -1.43392000 -1.22484000 H 2.48869100 1.47238800 -0.31628100 H 3.66478800 -0.75043900 -0.04743000 H -1.25024500 -1.28173900 1.42529600 C -0.38174000 1.49987900 0.15262000 H -0.05653300 2.37362000 0.70574800 H -2.99914700 -0.28223100 -0.88822800

TS8-9 C -1.38826700 -1.26522100 -0.09317900 C -0.00365100 -1.06595400 -0.19512800 C -2.27314500 -0.08899900 0.09318200 C -1.79090200 1.24158100 0.05778900

34

C 0.51003500 0.23015200 -0.08354100 C 1.95874900 0.49476300 -0.09776400 C 2.92535000 -0.37658100 0.20338000 H -1.82371900 -2.25245400 -0.22234900 H 2.71580200 -1.39761800 0.50406600 H 0.64595600 -1.91236600 -0.37967400 H 2.23367400 1.51633300 -0.34881300 H 3.96859600 -0.08519300 0.17500100 H -1.75173000 -0.81783300 1.05303600 C -0.39195600 1.32314900 -0.03177800 H 0.06391400 2.31064400 -0.11555800 H -3.32976600 -0.31884900 0.21651900

TS9-10 C 1.34040000 1.31999900 -0.02337600 C 0.00128100 1.09278800 -0.02285400 C 2.25207600 0.18844000 -0.00642400 C 1.81858900 -1.19511500 -0.08289500 C -0.50811800 -0.24981500 -0.01602100 C -1.95230600 -0.52551500 -0.01303800 C -2.94471500 0.36916400 0.03197800 H 1.73161500 2.33247100 -0.03914700 H -2.77461800 1.43890600 0.07541600 H -0.68837900 1.92842200 -0.03885900 H -2.20864500 -1.58139200 -0.04814800 H -3.97968700 0.04876400 0.02920500 H 2.29274200 -0.40039200 1.04299000 C 0.38514100 -1.30869300 -0.00722500 H -0.03484200 -2.31302600 -0.00944700 H 3.30772700 0.39872200 -0.17288500

TS11-14

C 1.55275700 -1.17787800 -0.12077500 C 0.14550600 -1.23428800 -0.11931600 C 2.24124500 0.01169100 0.03673100

35

C 1.50142400 1.22317200 -0.08359200 C -0.60151100 0.03349900 0.23822000 C -2.02683500 0.01316200 0.03500100 C -3.21040100 0.00431200 -0.17035200 H 2.09792200 -2.10384200 -0.27477700 H -0.42401000 -2.10973000 -0.39395100 H -0.14028300 -0.86841200 1.16522700 H -0.65395900 -0.03517600 1.77961100 H -4.25799200 -0.00226500 -0.34999000 H 2.04209600 2.15171700 -0.23954900 C 0.13778600 1.25481700 -0.07271800 H -0.42579600 2.16802000 -0.20609500 H 3.32219900 0.02876500 0.06033500

TS12-13

C -1.52751500 1.13819800 -0.32360200 C -0.11341200 1.19763000 0.26667000 C -2.18552600 -0.17876700 0.04462500 C -1.48688000 -1.39969900 0.05676400 C 0.63991900 -0.09473800 0.01197600 C 2.05960700 -0.03851800 -0.00700600 C 3.26348100 0.04392900 -0.02172200 H -2.12329900 1.99179000 0.00861300 H 0.44562700 2.03809000 -0.14992600 H -0.16414800 1.37080300 1.35176500 H -1.93573600 -0.75159600 1.15415600 H 4.32449500 0.10055400 -0.04001100 H -1.47417800 1.18644900 -1.41901000 C -0.03697100 -1.26265000 -0.14290700 H 0.52250200 -2.16872400 -0.35256100 H -3.27147300 -0.19967200 0.13818300

TS13-14

C 1.50092000 -1.16368900 -0.27904500 C 0.06743200 -1.17877000 0.22987800

36

C 2.18143800 0.05336900 -0.20893900 C 1.53219200 1.24404200 0.11485500 C -0.63774000 0.10639500 0.03705800 C -2.04405200 0.07919600 -0.08478800 C -3.24900200 0.01096000 -0.16797100 H 1.01379300 -1.31796100 1.07089000 H -0.46362900 -2.09821800 0.01128800 H 0.07808800 -1.39541000 1.60979900 H 2.08473000 2.17151200 0.17638700 H -4.30659900 -0.03184400 -0.25515300 H 1.93540400 -2.08294400 -0.64272300 C 0.11930600 1.26014700 0.09837700 H -0.39775300 2.21345000 0.07077100 H 3.23300200 0.07152500 -0.47780600

TS15-16

C 2.04062600 -0.59566600 -0.16146100 C -1.92912200 0.63038000 0.25752100 C 1.79964900 0.89503700 -0.12043200 C 0.47183800 0.82513400 0.14924900 C -1.68719500 -1.02547800 -0.33626800 C -0.50681500 -1.47005900 -0.12462300 C 0.61555300 -0.77048700 0.44955800 H 2.84596300 -0.99545900 0.46163300 H -2.02613600 0.38244900 1.31456600 H -2.87147800 0.99302300 -0.14829000 H -2.60285400 -1.43136700 -0.73538200 H 0.69598500 -0.96290900 1.52414600 H 2.14284300 -1.00348200 -1.17433000 C -0.77328600 1.38050800 -0.12411300 H -0.85045700 2.06658300 -0.96236400 H 2.47865600 1.73495500 -0.21656600

TS16- C 2.17138600 -0.00000300 0.16121500

37

17 C -2.17146100 0.00000800 -0.16099900 C 1.31778200 -1.22923000 -0.09273600 C 0.00001600 -1.00998200 -0.00018400 C -1.31773100 1.22930500 0.09257800 C -0.00000300 1.00996000 -0.00019300 C 1.31772500 1.22935700 -0.09255600 H 3.03188000 0.00010100 -0.51658300 H -2.60275500 -0.00000500 -1.17587300 H -3.03162400 -0.00005800 0.51723100 H -1.74655400 2.08248600 0.60931100 H 1.74652900 2.08259800 -0.60920600 H 2.60215400 -0.00011800 1.17632700 C -1.31766800 -1.22939400 0.09255600 H -1.74645800 -2.08237100 0.60965200 H 1.74656300 -2.08275300 -0.60894400

Table S5. Quantum chemical parameters for phenyl+acetylene reaction.Species Relativ

e ZEPEnergy(kcal/mol)

Frequencies (unscaled) (cm-1) RotationalConstants

(GHz)

<S2> External

symmetry

number

Optical

isomers

Electronic

ground

state

/ Å (/kB)/K

CS1 (phenyl) 0 399.7932 425.3889 602.0331 619.8493 666.3465 717.3815807.5801 887.6292 955.0698983.4880 988.9634 1015.3140

1050.2446 1073.6869 1178.95731179.4836 1308.0261 1327.68891466.4196 1475.5395 1575.92961630.0544 3154.8894 3160.8449

6.290595.615842.96705

0.7572(0.75)

1 1 Doublet 5.33506 459.2845

38

3173.7409 3176.3852 3187.3876

CS2 -38.0 84.0404 216.1063 224.2626412.7910 450.3810 462.1313462.1313 634.0534 638.7075705.0644 754.7566 770.0187839.9781 857.8020 882.6517935.5186 986.3220 1004.9826

1015.6225 1047.4340 1101.52921181.9141 1199.4337 1216.35311260.8669 1336.5382 1355.76801477.3841 1522.3811 1612.56391638.7096 1650.1606 3015.06183158.2733 3164.5602 3173.93673181.5051 3190.6834 3254.3254

5.297741.588911.22231

0.7627(0.75)

1 1 Doublet 5.74534 532.0455

CS3 (phenylacetylene)

-7.9 139.9758 159.2270 363.2094410.9162 473.8214 537.1889540.0885 587.2376 637.5011650.0589 703.6788 771.4051776.7455 848.8327 926.2562963.9927 990.5704 1017.1947

1051.2368 1103.7107 1187.69141205.4387 1225.1110 1314.41441359.6097 1480.1518 1529.62471616.3741 1647.7837 2208.32613164.7385 3174.0964 3185.28383193.9697 3198.0564 3466.9032

5.70001 1.53115 1.20694

0(0) 1 1 Doublet 5.72956 529.247

TS12 3.5 -298.0390 17.4547 60.328794.3203 206.1300 398.8819434.0024 518.7755 609.2669610.5801 617.2661 680.1540

4.94870 1.22941 1.03529

0.7698(0.75)

1 1 Doublet - -

39

718.8212 757.3232 760.8026825.3232 893.4500 956.6872980.5265 984.3439 1015.7223

1051.3452 1075.9585 1179.64471182.5464 1317.0516 1326.91931466.2787 1479.3459 1580.60871627.5282 1945.5302 3150.29483155.8988 3167.5878 3170.70903183.6571 3389.4371 3473.7921

TS23 -4.2 -696.4360 55.5521 152.5408217.9923 380.1545 410.1175470.6656 519.8779 544.1807554.1783 634.2861 645.2629679.1100 702.3792 774.6224778.1943 853.4149 938.5360

987.6213 1006.1039 1015.05251048.1428 1101.5727 1183.46211198.0950 1210.6733 1315.50941350.8357 1472.1069 1517.93621609.6536 1637.8816 2106.62103166.2958 3175.4916 3185.89123193.8794 3197.4448 3462.5488

5.39096 1.51116 1.18711

0.7626(0.75)

1 1 Doublet - -

Table S6. Cartesian coordinates of optimized structures at B3LYP/6-311+G(d,p) level for phenyl+acetylene reaction.Species Geometry(Ǻ)CS1 C -2.75849700 -3.30816204 0.00125800

C -1.36333700 -3.30816204 0.00125800 C -0.66579900 -2.10041104 0.00125800 C -1.36345300 -0.89190204 0.00005900 C -2.75827800 -0.89198004 -0.00042000

40

C -3.45587900 -2.10018604 0.00057600 H -3.30825600 -4.26047904 0.00170800 H -0.81382900 -4.26067504 0.00257300 H 0.43388100 -2.10033104 0.00189200 H -0.81325300 0.06024096 0.00000000 H -3.30840000 0.06030096 -0.00137300

CS2 C -1.32536200 1.32273100 0.00002300 C 0.04644800 1.10624700 0.00000400 C 0.56478200 -0.19893600 -0.00000800 C -0.33286000 -1.27486300 0.00000400 C -1.70918100 -1.05743800 0.00002100 C -2.21062000 0.24174900 0.00003200 H -1.70946600 2.33686500 0.00003100 H 0.73142400 1.94662000 -0.00000300 H 0.05236000 -2.28947800 -0.00000300 H -2.38817900 -1.90282200 0.00002800 H -3.28098500 0.41369000 0.00004700 C 2.01539500 -0.46156100 -0.00003200 C 2.99006900 0.42094800 -0.00005200 H 2.29402600 -1.52248200 0.00001000 H 4.06878700 0.42434600 -0.00005300

CS3 C 1.51273500 -1.20853700 0.00021100C 0.12002000 -1.21289700 0.00019200C -0.59414600 -0.00004000 -0.00000500C 0.12013000 1.21318900 -0.00019200C 1.51257500 1.20854400 -0.00017000C 2.21319900 -0.00006400 0.00003600H 2.05292200 -2.15138700 0.00036800H -0.42808100 -2.15003600 0.00033100H -0.42878000 2.14979400 -0.00035000H 2.05297200 2.15130800 -0.00031400

41

H 3.29977700 0.00012400 0.00005100C -2.02448200 0.00009100 -0.00002900C -3.23469000 -0.00056600 -0.00004900H -4.30086100 0.00186800 -0.00005100

TS12 C -1.66486900 -1.21028600 0.06192900 C -0.27145300 -1.22028400 -0.08888700 C 0.36868000 -0.00164300 -0.16610600 C -0.26858900 1.21865000 -0.09138200 C -1.66201400 1.21222100 0.05951100 C -2.35268200 0.00185200 0.13479100 H -2.20739100 -2.14943700 0.12422700 H 0.27409600 -2.15772000 -0.14084900 H 0.27918400 2.15466000 -0.14543900 H -2.20234400 2.15276100 0.11986900 H -3.43152700 0.00324000 0.25319100 C 2.71365300 -0.00365200 -0.50010600 C 3.31817000 0.00270000 0.55373400 H 2.53229900 -0.00967900 -1.55108100 H 3.67030500 0.00882800 1.55917600

TS23 C 1.47410200 -1.26618600 0.00024200C 0.08518100 -1.18024200 0.00020900C -0.55251800 0.07704100 -0.00007400C 0.23771200 1.23819700 -0.00020500C 1.62773900 1.14425300 -0.00019800C 2.25099900 -0.10477400 -0.00005500H 1.95130700 -2.24240500 0.00045400H -0.52320100 -2.07920600 0.00042500H -0.25082500 2.20763300 -0.00024600H 2.22541700 2.05165300 -0.00032600H 3.33539100 -0.17386500 -0.00004900C -1.99311900 0.10917100 -0.00025100

42

C -3.15929100 -0.25877100 -0.00047700H -2.34549200 2.07787900 0.00426100H -4.21743800 -0.39382600 0.00033300

Reference.1. Watts, J.D., J. Gauss, and R.J. Bartlett, Coupled cluster methods with noniterative triple excitations for restricted open shell Hartree–Fock and other general single determinant‐ ‐

reference functions. Energies and analytical gradients. The Journal of chemical physics, 1993. 98(11): p. 8718-8733.2. Lee, T.J. and P.R. Taylor, A diagnostic for determining the quality of single reference electron correlation methods.‐ International Journal of Quantum Chemistry, 1989. 36(S23): p. 199-

207.3. Celani, P. and H.-J. Werner, Multireference perturbation theory for large restricted and selected active space reference wave functions. The Journal of Chemical Physics, 2000.

112(13): p. 5546-5557.4. Yamamoto, N., et al., A direct derivative MC-SCF procedure. Chemical physics letters, 1996. 250(3): p. 373-378.5. Guner, V., et al., A Standard Set of Pericyclic Reactions of Hydrocarbons for the Benchmarking of Computational Methods:  The Performance of ab Initio, Density Functional, CASSCF,

CASPT2, and CBS-QB3 Methods for the Prediction of Activation Barriers, Reaction Energetics, and Transition State Geometries. The Journal of Physical Chemistry A, 2003. 107(51): p. 11445-11459.

43