Electronic Supplementary Material (ESI) for Physical ... · Electronic Supplementary Material (ESI)...

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.

Supplementary Information

Table S1. B3LYP and CCSD(T) calculated total energies at 0 K, zero-point energy corrections (ZPE), B3LYP/6-311G** optimized Cartesian coordinates, unscaled vibrational frequencies (vi), moments of inertia (Ii), and rotational constants (Bi) of all species involved in the studied C4 + C2H2 reactions.

Species,(point group),electronic state

Energies, a.u. i Ii, a.u. Bi, GHz Cartesian coordinates, angstroms vi, cm-1

Atom X Y ZH ZPE(B3LYP/6-311G**) = 0.0

E(B3LYP/6-311G**) = -0.502156E(CCSD(T)/cc-pVDZ) = -0.499278E(CCSD(T)/cc-pVTZ) = -0.499810E(CCSD(T)/cc-pVQZ) = -0.499946

H2

(Dh)1Σg

+

ZPE(B3LYP/6-311G**) = 0.010068E(B3LYP/6-311G**) = -1.179571E(CCSD(T)/cc-pVDZ) = -1.163484E(CCSD(T)/cc-pVTZ) = -1.172335E(CCSD(T)/cc-pVQZ) = -1.173793

ABC

0.0 1.01.0

1810.980 HH

0.0000000.000000

0.0000000.000000

0.372087-0.372087

4419

C2

(Dh)1Σg

+

ZPE(B3LYP/6-311G**) = 0.004264E(B3LYP/6-311G**) = -75.900548E(CCSD(T)/cc-pVDZ) = -75.727307E(CCSD(T)/cc-pVTZ) = -75.782644E(CCSD(T)/cc-pVQZ) = -75.800777

ABC

0.033.633.6

53.78456 CC

0.0000000.000000

0.0000000.000000

0.625712-0.625712

1872

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.This journal is © the Owner Societies 2019

C2

(Dh)3u

ZPE(B3LYP/6-311G**) = 0.003855E(B3LYP/6-311G**) = -75.936669E(CCSD(T)/cc-pVDZ) = -75.723943 E(CCSD(T)/cc-pVTZ) = -75.780066E(CCSD(T)/cc-pVQZ) = -75.797204

ABC

0.036.536.5

49.40797 CC

0.0000000.000000

0.0000000.000000

0.652837-0.652837

1692

C2H(Cv)2Σg

ZPE(B3LYP/6-311G**) = 0.014018E(B3LYP/6-311G**) = -76.629459E(CCSD(T)/cc-pVDZ) = -76.398274E(CCSD(T)/cc-pVTZ) = -76.467245E(CCSD(T)/cc-pVQZ) = -76.487261

ABC

0.0 40.5 40.5

44.51304 CHC

0.0000000.0000000.000000

0.0000000.0000000.000000

-0.472997-1.537132 0.729185

301, 301, 2090, 3461

C2H2

(Dh)1Σg

+

ZPE(B3LYP/6-311G**) = 0.026984E(B3LYP/6-311G**) = -77.354698E(CCSD(T)/cc-pVDZ) = -77.108684E(CCSD(T)/cc-pVTZ) = -77.187394E(CCSD(T)/cc-pVQZ) = -77.209184

ABC

0.050.650.6

35.63882 CHCH

0.0000000.0000000.0000000.000000

0.0000000.0000000.0000000.000000

0.599072 1.661935-0.599072-1.661935

642, 642, 773, 773, 2070, 3421, 3524

C3H(Dh)1Σg

+

ZPE(B3LYP/6-311G**) = E(B3LYP/6-311G**) = E(CCSD(T)/cc-pVDZ) = E(CCSD(T)/cc-pVTZ) = E(CCSD(T)/cc-pVQZ) =

ABC

l-C4

(Dh)3Σg

-

ZPE(B3LYP/6-311G**) = 0.012953E(B3LYP/6-311G**) = -152.128365E(CCSD(T)/cc-pVDZ) = -151.664476E(CCSD(T)/cc-pVTZ) = -151.790096E(CCSD(T)/cc-pVQZ) = -151.827447

ABC

0.0362.9362.9

4.973210 CCCC

0.0000000.0000000.0000000.000000

0.0000000.0000000.0000000.000000

0.644565 1.954153-0.644565-1.954153

170, 170, 347, 347, 938, 1592, 2123

l-C4

(Dh)1Σu

+

ZPE(B3LYP/6-311G**) = 0.013097E(B3LYP/6-311G**) = -152.099927E(CCSD(T)/cc-pVDZ) = -151.650102

ABC

0.0364.1364.1

4.957172 CCC

0.0000000.0000000.000000

0.0000000.0000000.000000

-0.646445-1.956972 0.646257

147, 207, 272, 463, 935, 1598, 2126

E(CCSD(T)/cc-pVTZ) = -151.775835E(CCSD(T)/cc-pVQZ) = -151.813465

C 0.000000 0.000000 1.957160

r-C4

(D2h)1Ag

ZPE(B3LYP/6-311G**) = 0.012458E(B3LYP/6-311G**) = -152.1028395E(CCSD(T)/cc-pVDZ) = -151.667472E(CCSD(T)/cc-pVTZ) = -151.791190E(CCSD(T)/cc-pVQZ) = -151.829931

ABC

48.0131.5179.5

37.64676 13.72477 10.05797

CCCC

-0.000195 1.238693 0.000119-1.238617

0.748082-0.000095-0.747703-0.000284

0.000037 0.000025-0.000009-0.000053

309, 499, 952, 1014, 1295, 1400

r-C4

(D2d)3A1

ZPE(B3LYP/6-311G**) = 0.010691E(B3LYP/6-311G**) = -152.061180E(CCSD(T)/cc-pVDZ) = -151.624259E(CCSD(T)/cc-pVTZ) = -151.745316E(CCSD(T)/cc-pVQZ) = -151.783375

ABC

88.588.5

163.5

20.37437 20.37437 11.02505

CCCC

0.000000-0.977232 0.000000 0.977232

0.977232 0.000000-0.977232 0.000000

0.198171-0.198171 0.198171-0.198171

621, 649, 659, 718, 718, 1327

C4H(Cv),2

ZPE(B3LYP/6-311G**) = 0.023899E(B3LYP/6-311G**) = -152.812211E(CCSD(T)/cc-pVDZ) = -152.337464 E(CCSD(T)/cc-pVTZ) = -152.474221E(CCSD(T)/cc-pVQZ) = -152.514000

ABC

0.0 391.0 391.0

4.615643 CHCCC

0.0000000.0000000.0000000.0000000.000000

0.0000000.0000000.0000000.0000000.000000

-1.800471-2.874121-0.564459 0.773859 2.070092

7, 228, 432, 521, 576, 725, 930, 1858, 2130, 3461

C4H2

(Dh),1Σg

+

ZPE(B3LYP/6-311G**) = 0.037455E(B3LYP/6-311G**) = -153.528450E(CCSD(T)/cc-pVDZ) = -153.047958E(CCSD(T)/cc-pVTZ) = -153.195970E(CCSD(T)/cc-pVQZ) = -153.237991

ABC

0.0408.5408.5

4.417859 CHCCCH

0.0000000.0000000.0000000.0000000.0000000.000000

0.0000000.0000000.0000000.0000000.0000000.000000

1.889132 2.951514 0.682633-0.682633-1.889132-2.951514

235, 235, 527, 527, 662, 662, 663, 663, 917, 2111, 2285, 3476, 3478

l-C6H(Cv),2

ZPE(B3LYP/6-311G**) = 0.034976E(B3LYP/6-311G**) = -228.996397E(CCSD(T)/cc-pVDZ) = -228.279459E(CCSD(T)/cc-pVTZ) = -228.485627E(CCSD(T)/cc-pVQZ) = -228.545330

ABC

0.01298.21298.2

-1.39020 1.39020

CHCCC

0.0000000.0000000.0000000.0000000.000000

0.0000000.0000000.0000000.0000000.000000

-3.064150-4.127679-1.846396-0.511491 0.731925

77, 109, 174, 246, 387, 461, 562, 574, 588, 650, 702, 1225, 1896, 2105, 2137, 3461

CC

0.0000000.000000

0.0000000.000000

2.045617 3.332442

HC3C3

(Cs),2A”

ZPE(B3LYP/6-311G**) = 0.033611E(B3LYP/6-311G**) = -228.938643E(CCSD(T)/cc-pVDZ) = -228.231494E(CCSD(T)/cc-pVTZ) = -228.433471E(CCSD(T)/cc-pVQZ) = -228.493328

ABC

48.7973.6

1022.3

37.06600 1.85374 1.76544

CCCCCHC

-0.116752-0.240468 0.111123 0.000000 0.915810-1.402121-0.436027

1.778636 3.071963-0.795327 0.505431-2.066209-2.548937-2.069670

0.0000000.0000000.0000000.0000000.0000000.0000000.000000

116, 131, 259, 341, 470, 565, 611, 794, 881, 975, 1117, 1449, 1756, 2026, 3262

c-C6H(C2v),2A1

ZPE(B3LYP/6-311G**) = 0.036934E(B3LYP/6-311G**) = -228.960754E(CCSD(T)/cc-pVDZ) = -228.268218E(CCSD(T)/cc-pVTZ) = -228.471426 E(CCSD(T)/cc-pVQZ) = -228.533301

ABC

233.9241.6475.5

7.71735 7.46851 3.79545

CCCCCCH

0.0000000.0000000.0000000.0000000.0000000.0000000.000000

1.066214 0.000000-1.066214-1.297184 0.000000 1.297184 0.000000

0.489498 1.372042 0.489498-0.818556-1.121948-0.818556 2.448137

366, 431, 512, 536, 557, 688, 737, 940, 1099, 1134, 1199, 1292, 1714, 1734, 3272

l-C6

(Dh),1Σg

+

ZPE(B3LYP/6-311G**) = 0.023511E(B3LYP/6-311G**) = -228.292261E(CCSD(T)/cc-pVDZ) = -227.599780 E(CCSD(T)/cc-pVTZ) = -227.795414E(CCSD(T)/cc-pVQZ) = -227.853093

ABC

0.01243.91243.9

1.450901 CCCCCC

0.0000000.0000000.0000000.0000000.0000000.000000

0.0000000.0000000.0000000.0000000.0000000.000000

-3.224681-1.925851-0.637081 0.637092 1.925812 3.224710

93, 112, 180, 237, 333, 422, 425, 652, 667, 1229, 1740, 2043, 2186

c-C6

(D3h),1A1’

ZPE(B3LYP/6-311G**) = 0.027400E(B3LYP/6-311G**) = -228.303692E(CCSD(T)/cc-pVDZ) = -227.618805E(CCSD(T)/cc-pVTZ) = -227.820660E(CCSD(T)/cc-pVQZ) = -227.882762

ABC

216.3216.3432.6

8.34423 8.34423 4.17211

CCCCCC

0.000000 1.270028-1.270028-0.954267 0.954267 0.000000

1.101892 0.733251 0.733251-0.550946-0.550946-1.466502

0.0000000.0000000.0000000.0000000.0000000.000000

431, 535, 535, 635, 643, 643, 1220, 1231, 1231, 1406, 1759, 1759

r-i1(Cs),3A”

ZPE(B3LYP/6-311G**) = 0.038358E(B3LYP/6-311G**) = -229.427159E(CCSD(T)/cc-pVDZ) = -228.738779E(CCSD(T)/cc-pVTZ) = -228.939403E(CCSD(T)/cc-pVQZ) = -228.999898

ABC

102.61121.01223.6

17.58953 1.60996 1.47496

CCCCCHCH

-0.355409-1.787124-1.386908 0.000000 1.117649 0.401109 1.903838 2.646611

1.779244 2.029955 0.628559 0.409223-2.530354-3.316247-1.620593-0.859961

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

19, 34, 39, 50, 98, 364, 577, 649, 660, 694, 763, 773, 794, 1058, 1286, 2041, 3419, 3519

r-i2(Cs),3A”

ZPE(B3LYP/6-311G**) = 0.043480E(B3LYP/6-311G**) = -229.510619E(CCSD(T)/cc-pVDZ) = -228.819277E(CCSD(T)/cc-pVTZ) = -229.019500E(CCSD(T)/cc-pVQZ) = -229.080186

ABC

87.7702.2789.9

20.57199 2.57012 2.28468

CCCCCHCH

-1.399185-2.191437-0.766575 0.000000 2.424509 2.745794 1.262610 1.274668

0.404224-0.806522-0.962856 0.230034 0.142633-0.888065 0.822115 1.910292

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

162, 186, 265, 440, 510, 617, 660, 724, 749, 866, 910, 1068, 1239, 1310, 1444, 1558, 3130, 3246

3i1(Cs),3A”

ZPE(B3LYP/6-311G**) = 0.040677E(B3LYP/6-311G**) = -229.485036E(CCSD(T)/cc-pVDZ) = -228.775327E(CCSD(T)/cc-pVTZ) = -228.979656E(CCSD(T)/cc-pVQZ) = -229.038964

ABC

241.41164.81406.2

7.47587 1.54942 1.28342

CHCCCHCC

-1.612240-2.586617-0.515567-1.282840 0.000000 0.454999 1.248622 2.517295

-2.088507-1.663540-2.576516 0.927609 1.184533-3.010526 1.508483 1.823410

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

30, 39, 42, 113, 176, 199, 359, 388, 654, 654, 773, 780, 941, 1601, 2052, 2111, 3420, 3522

3i2(Cs),3A”

ZPE(B3LYP/6-311G**) = 0.044779E(B3LYP/6-311G**) = -229.561353E(CCSD(T)/cc-pVDZ) = -228.846220E(CCSD(T)/cc-pVTZ) = -229.050892

ABC

49.81181.41231.2

36.25888 1.52757 1.46582

CHCC

0.553003-0.107843 1.883330 0.000000

1.889530 2.755836 2.053127 0.610345

0.0000000.0000000.0000000.000000

91, 97, 211, 237, 423, 491, 493, 705, 736, 859, 911, 1233, 1274, 1475, 1919, 2164, 3107, 3229

E(CCSD(T)/cc-pVQZ) = -229.110721 CHCC

-0.464426 2.744065-0.963487-1.447790

-0.538849 1.397915-1.759025-2.947421

0.0000000.0000000.0000000.000000

3i3(C2v),3A2

ZPE(B3LYP/6-311G**) = 0.043761E(B3LYP/6-311G**) = -229.598806E(CCSD(T)/cc-pVDZ) = -228.873973E(CCSD(T)/cc-pVTZ) = -229.082045E(CCSD(T)/cc-pVQZ) = -229.142202

ABC

6.21354.01360.2

291.6152 1.33292 1.32686

CHCCCHCC

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

0.000000 0.927248 0.000000 0.000000 0.000000-0.927248 0.000000 0.000000

-1.712656-3.614294-3.045208-0.447777 0.845364-3.614294 2.129420 3.435622

95, 95, 182, 201, 348, 392, 408, 588, 647, 899, 1016, 1168, 1455, 1626, 1867, 1966, 3090, 3168

3i4(Cs),3A”

ZPE(B3LYP/6-311G**) = 0.042266E(B3LYP/6-311G**) = -229.597180E(CCSD(T)/cc-pVDZ) = -228.863252E(CCSD(T)/cc-pVTZ) = -229.075580E(CCSD(T)/cc-pVQZ) = -229.136757

ABC

2.71350.61353.4

661.1576 1.33621 1.33352

CCCCCCHH

0.024616-0.025144 0.088567 0.000208 0.000000-0.088383-0.585497 0.586310

3.196669-3.196784-1.929194-0.642343 0.642299 1.929225 4.083427-4.082657

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

103, 110, 249, 273, 341, 377, 405, 471, 588, 598, 679, 759, 1262, 1728, 1864, 2180, 3281, 3282

3i5(Cs),3A”

ZPE(B3LYP/6-311G**) = 0.044308E(B3LYP/6-311G**) = -229.579795E(CCSD(T)/cc-pVDZ) = -228.864133E(CCSD(T)/cc-pVTZ) = -229.070994E(CCSD(T)/cc-pVQZ) = -229.131560

ABC

46.71182.81229.6

38.61378 1.52580 1.46780

CHCCCHCC

0.007795 1.751341-0.527462 0.658766 0.000000-1.011279-0.046594-0.215849

-1.763956-0.551112-2.852214-0.532201 0.669076-3.799574 1.949877 3.254532

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

78, 119, 235, 278, 383, 403, 516, 665, 669, 825, 902, 1090, 1297, 1481, 1870, 2108, 3068, 3462

3i6(C1),3A

ZPE(B3LYP/6-311G**) = 0.042823E(B3LYP/6-311G**) = -229.571645E(CCSD(T)/cc-pVDZ) = -228.853046E(CCSD(T)/cc-pVTZ) = -229.059619E(CCSD(T)/cc-pVQZ) = -229.120183

ABC

98.21054.71152.5

18.38646 1.71111 1.56587

CHCCCHCC

1.686063-1.048405 2.855312 0.484664-0.819099 3.834865-1.851279-2.820071

-0.028669 1.900325-0.452514 0.454981 0.832916-0.867194-0.074452-0.904451

-0.002183-0.047611 0.000593-0.008047-0.004703 0.005748 0.051777-0.030459

22, 147, 201, 219, 236, 368, 476, 507, 610, 818, 854, 1050, 1333, 1634, 1847, 1958, 3069, 3449

3i7(Cs),3A”

ZPE(B3LYP/6-311G**) = 0.043642E(B3LYP/6-311G**) = -229.559050E(CCSD(T)/cc-pVDZ) = -228.841111E(CCSD(T)/cc-pVTZ) = -229.048844E(CCSD(T)/cc-pVQZ) = -229.109074

ABC

50.31183.51233.8

35.90529 1.52491 1.46278

CHCCCHCC

-0.544425 2.054085-1.037312 0.000000 0.511672-1.470354 0.972608 0.000168

1.749574-2.069733 2.861346 0.525068-0.602666 3.832477-1.890315-2.936798

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

105, 147, 224, 313, 409, 458, 522, 563, 599, 677, 737, 1121, 1244, 1372, 2065, 2117, 3017, 3464

3i8(Cs),3A”

ZPE(B3LYP/6-311G**) = 0.044380E(B3LYP/6-311G**) = -229.538519E(CCSD(T)/cc-pVDZ) = -228.829832E(CCSD(T)/cc-pVTZ) = -229.037567E(CCSD(T)/cc-pVQZ) = -229.098593

ABC

147.9 760.9 908.8

12.20195 2.37185 1.98583

CHCCCHCC

1.376359-1.757650 2.583965 0.000000-1.210667 3.647104-1.223416-1.841149

0.387743 1.802655 0.405162 0.286398 0.870321 0.428874-0.536313-1.785232

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

137, 138, 239, 332, 464, 523, 617, 635, 726, 815, 838, 970, 1030, 1455, 1703, 2171, 3221, 3467

3i9(C1),3A

ZPE(B3LYP/6-311G**) = 0.044628E(B3LYP/6-311G**) = -229.537945E(CCSD(T)/cc-pVDZ) = -228.833752E(CCSD(T)/cc-pVTZ) = -229.040839

ABC

74.1764.8825.6

24.36639 2.36044 2.18596

CHCC

-1.412218 1.281602-2.626338-0.048484

-0.029614 1.707723-0.001550-0.048794

-0.008299 0.568519-0.043820-0.025888

140, 180, 400, 493, 517, 547, 608, 698, 753, 847, 901, 987, 1102, 1283, 1486, 2083, 3097, 3468

E(CCSD(T)/cc-pVQZ) = -229.102757 CHCC

1.144520-3.688607 1.115477 2.228209

0.787842 0.019749-0.823426-0.172370

-0.001418-0.065464 0.250082-0.254500

3i10(Cs),3A”

ZPE(B3LYP/6-311G**) = 0.042888E(B3LYP/6-311G**) = -229.582402E(CCSD(T)/cc-pVDZ) = -228.864971E(CCSD(T)/cc-pVTZ) = -229.074090E(CCSD(T)/cc-pVQZ) = -229.135376

ABC

51.31024.91076.2

35.17498 1.76096 1.67701

CCCCCCHH

-0.283579 0.798356-0.586052 0.076933 0.000000-0.194544-0.652312 1.785627

2.936315-2.082012-2.245919-0.937353 0.412972 1.680320 3.935489-2.521432

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

64, 119, 242, 373, 399, 410, 473, 502, 609, 846, 935, 982, 1215, 1456, 1714, 1838, 3223, 3425

r-TS1(Cs),3A”

ZPE(B3LYP/6-311G**) = 0.038520E(B3LYP/6-311G**) = -229.427092E(CCSD(T)/cc-pVDZ) = -228.736462E(CCSD(T)/cc-pVTZ) = -228.937695E(CCSD(T)/cc-pVQZ) = -228.998335

ABC

98.61040.51139.1

18.30850 1.73452 1.58442

CCCCCHCH

-0.359475-1.792142-1.382638 0.000000 1.184634 0.557760 1.834593 2.532407

1.691436 1.952868 0.550921 0.324964-2.441224-3.300800-1.425107-0.622344

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

83i, 23, 48, 51, 155, 349, 569, 649, 654, 708, 769, 778, 816, 1112, 1290, 2014, 3413, 3509

3TS1(Cs),3A”

ZPE(B3LYP/6-311G**) = 0.041105E(B3LYP/6-311G**) = -229.482925E(CCSD(T)/cc-pVDZ) = -228.767261E(CCSD(T)/cc-pVTZ) = -228.972638E(CCSD(T)/cc-pVQZ) = -229.032464

ABC

148.71064.71213.4

12.13784 1.69512 1.48740

CHCCCHCC

-1.484579-2.545424-0.340098-1.190811 0.000000 0.695829 1.102056 2.221698

-1.905153-1.824606-2.308668 0.340892 0.858303-2.553170 1.542515 2.201741

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

262i, 65, 76, 182, 193, 262, 385, 486, 643, 666, 777, 808, 956, 1639, 1961, 2037, 3409, 3498

3TS2(Cs),3A”

ZPE(B3LYP/6-311G**) = 0.035614E(B3LYP/6-311G**) = -229.489941E(CCSD(T)/cc-pVDZ) = -228.766836E(CCSD(T)/cc-pVTZ) = -228.974354E(CCSD(T)/cc-pVQZ) = -229.034684

ABC

17.31307.01324.3

104.5364 1.38083 1.36282

CHCCCHCC

0.042322 1.925220-0.311388 0.000000 0.009649-0.348403 0.000457-0.003843

1.805297 1.938737 2.988775 0.462233-0.780089 4.053495-2.094112-3.380810

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

880i, 76, 106, 181, 243, 407, 436, 475, 512, 553, 558, 678, 761, 1214, 1869, 1996, 2131, 3435

3TS3(C1),3A

ZPE(B3LYP/6-311G**) = 0.037828E(B3LYP/6-311G**) = -229.492266E(CCSD(T)/cc-pVDZ) = -228.768663 E(CCSD(T)/cc-pVTZ) = -228.976542E(CCSD(T)/cc-pVQZ) = -229.037088

ABC

12.71321.01329.3

142.6093 1.36623 1.35770

CHCCCHCC

-1.775391-2.519656-3.039499-0.454983 0.798054-3.633063 2.104687 3.392584

0.201833 1.054687-0.134445-0.000232 0.004084-1.022342-0.023424-0.053207

-0.114958 0.452237 0.042217-0.093144-0.036731 0.272340 0.009097 0.072755

1919i, 85, 105, 163, 226, 314, 471, 500, 516, 643, 663, 850, 1184, 1691, 1884, 2039, 2218, 3053

3TS4(C1),3A

ZPE(B3LYP/6-311G**) = 0.037809E(B3LYP/6-311G**) = -229.452476E(CCSD(T)/cc-pVDZ) = -228.734355E(CCSD(T)/cc-pVTZ) = -228.935053E(CCSD(T)/cc-pVQZ) = -228.991635

ABC

176.8589.4766.3

10.20599 3.06190 2.35529

CHCCCHCC

-1.108380-0.163466-2.343462-0.196544 1.065035-3.145639 1.811827 1.323042

-0.017364 1.014015 0.281061-1.096035-0.956572 0.988328 0.129470 1.325715

-0.000165 0.000259 0.000151-0.000553 0.000406 0.000924 0.000344-0.000380

1575i, 124, 235, 272, 303, 414, 420, 481, 571, 622, 879, 946, 1308, 1417, 1663, 1762, 1803, 3377

3TS5(C1),3A

ZPE(B3LYP/6-311G**) = 0.037023E(B3LYP/6-311G**) = -229.487500E(CCSD(T)/cc-pVDZ) = -228.760556E(CCSD(T)/cc-pVTZ) = -228.968868

ABC

8.81317.91326.7

205.0831 1.36942 1.36034

CHCC

1.820333 1.201788 3.067614 0.489076

0.052542 1.252010-0.239092 0.050821

0.000031 0.000024 0.000079-0.000126

1658i, 87, 106, 183, 278, 395, 399, 468, 548, 629, 675, 741, 1202, 1617, 1705, 1927, 1995, 3296

E(CCSD(T)/cc-pVQZ) = -229.029485 CHCC

-0.785883 3.997650-2.079020-3.378692

-0.083923 0.301942-0.029147-0.010194

-0.000110 0.000170-0.000100 0.000193

3TS8(Cs),3A”

ZPE(B3LYP/6-311G**) = 0.035532E(B3LYP/6-311G**) = -229.493943E(CCSD(T)/cc-pVDZ) = -228.774484E(CCSD(T)/cc-pVTZ) = -228.982605E(CCSD(T)/cc-pVQZ) = -229.042999

ABC

24.41282.51306.9

73.91925 1.40723 1.38094

CHCCCHCC

0.721182-1.833325 1.352976 0.000000-0.285090 1.914744-0.704328-1.098310

1.668844 1.486649 2.708479 0.536226-0.686594 3.611742-1.924236-3.152450

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

657i, 90, 114, 193, 255, 358, 387, 464, 519, 524, 581, 676, 709, 1221, 1857, 2078, 2110, 3461

3TS9(C1),3A

ZPE(B3LYP/6-311G**) = 0.035217E(B3LYP/6-311G**) = -229.492116E(CCSD(T)/cc-pVDZ) = -228.768604E(CCSD(T)/cc-pVTZ) = -228.976503E(CCSD(T)/cc-pVQZ) = -229.036908

ABC

18.61294.21312.9

96.85123 1.39443 1.37464

CHCCCHCC

-1.859714 0.723384-3.079980-0.529717 0.714205-4.143611 2.024694 3.300550

-0.058436 2.086335-0.078330-0.061513 0.120864-0.090917-0.046236-0.208919

-0.000397 0.000471 0.000544-0.000596-0.000421 0.001353 0.000053 0.000513

802i, 63, 104, 161, 242, 390, 409, 459, 513, 526, 558, 672, 691, 1217, 1859, 2045, 2090, 3459

3TS10(C1),3A

ZPE(B3LYP/6-311G**) = 0.038381E(B3LYP/6-311G**) = -229.489068E(CCSD(T)/cc-pVDZ) = -228.768134E(CCSD(T)/cc-pVTZ) = -228.976231E(CCSD(T)/cc-pVQZ) = -229.037227

ABC

65.91156.11216.7

27.40084 1.56107 1.48334

CHCCCHCC

-1.742727 0.155981-2.897908-0.546513 0.794816-3.888776 1.907687 3.106778

-0.053242 1.376683-0.451140 0.563970 0.588324-0.835455-0.130394-0.607724

-0.019258 0.713312 0.033768-0.078636-0.118136 0.073671 0.011950 0.039148

1776i, 69, 199, 234, 242, 357, 453, 492, 533, 605, 697, 726, 1132, 1659, 1873, 2009, 2108, 3459

3TS11(C1),3A

ZPE(B3LYP/6-311G**) = 0.037372E(B3LYP/6-311G**) = -229.489903E(CCSD(T)/cc-pVDZ) = -228.766867E(CCSD(T)/cc-pVTZ) = -228.974169E(CCSD(T)/cc-pVQZ) = -229.034585

ABC

9.51312.11321.6

189.2430 1.37549 1.36557

CHCCCHCC

-1.877149 1.331221-3.096755-0.574089 0.680217-4.148895 2.004395 3.332993

-0.046436 1.212287 0.096314-0.287300-0.005331 0.248345 0.034005-0.034690

0.000157 0.000157 0.000049-0.000047-0.000030 0.000052-0.000740 0.000577

1461i, 85, 85, 224, 271, 365, 402, 457, 590, 607, 663, 718, 1172, 1603, 1641, 1992, 2067, 3461

3TS12(C1),3A

ZPE(B3LYP/6-311G**) = 0.042742E(B3LYP/6-311G**) = -229.533495E(CCSD(T)/cc-pVDZ) = -228.818296E(CCSD(T)/cc-pVTZ) = -229.025716E(CCSD(T)/cc-pVQZ) = -229.086624

ABC

138.8 814.6953.4

13.00354 2.21547 1.89296

CHCCCHCC

1.489877-1.130245 2.642992 0.169013-0.879633 3.659544-1.492380-2.351419

-0.006967 2.177897-0.398154 0.287214 1.122727-0.709276-0.109079-1.140511

0.004536-0.001773-0.002415 0.001898-0.001051-0.006358-0.002174 0.000561

604i, 119, 160, 237, 321, 443, 480, 516, 726, 808, 829, 912, 1160, 1627, 1712, 2077, 3171, 3464

3TS13(C1),3A

ZPE(B3LYP/6-311G**) = 0.038432E(B3LYP/6-311G**) = -229.517513E(CCSD(T)/cc-pVDZ) = -228.798137E(CCSD(T)/cc-pVTZ) = -229.005153E(CCSD(T)/cc-pVQZ) = -229.065287

ABC

10.91330.01337.3

165.8422 1.35697 1.34954

CCCCCCHH

-3.155848 3.266935 1.988595 0.670088-0.608072-1.898795-4.133219 2.555796

-0.047082-0.299374 0.108680 0.062546 0.024516-0.017681-0.109766 1.120135

-0.128781-0.046835-0.019881 0.111492 0.051803-0.000513 0.306474-0.110181

302i, 67, 115, 250, 266, 350, 387, 430, 464, 554, 644, 800, 1203, 1520, 1746, 2191, 2549, 3336

3TS14(C1),3A

ZPE(B3LYP/6-311G**) = 0.043055E(B3LYP/6-311G**) = -229.494941E(CCSD(T)/cc-pVDZ) = -228.791253E(CCSD(T)/cc-pVTZ) = -228.995989

ABC

122.5 714.4836.9

14.72945 2.52615 2.15645

CHCC

-1.337209 0.695200-2.537285 0.071268

-0.064713 2.242879-0.163596 0.064448

-0.000246 0.007059 0.005854-0.008741

511i, 14, 174, 263, 476, 547, 562, 691, 693, 715, 819, 935, 1220, 1493, 1512, 2205, 3111, 3469

E(CCSD(T)/cc-pVQZ) = -229.056698 CHCC

0.878394-3.596642 1.096220 2.312186

1.168135-0.256904-0.938527-0.396742

-0.004491 0.011189-0.011830 0.016413

3TS15(C1),3A

ZPE(B3LYP/6-311G**) = 0.040687E(B3LYP/6-311G**) = -229.508576E(CCSD(T)/cc-pVDZ) = -228.794734E(CCSD(T)/cc-pVTZ) = -229.003380E(CCSD(T)/cc-pVQZ) = -229.064921

ABC

73.4862.4920.3

24.59205 2.09279 1.96107

CHCCCHCC

-1.524165 1.391360-2.736117-0.214665 1.551164-3.787707 1.030039 2.293136

-0.082094 1.745357 0.121418-0.229969 0.812596 0.266148-0.677324-0.279878

0.012377 0.498383-0.085526 0.047919-0.018542-0.134323 0.267360-0.284264

470i, 88, 150, 265, 318, 380, 408, 509, 636, 671, 741, 911, 999, 1413, 1698, 1962, 3248, 3462

3TS16(Cs),3A”

ZPE(B3LYP/6-311G**) = 0.041927E(B3LYP/6-311G**) = -229.538254E(CCSD(T)/cc-pVDZ) = -228.812862E(CCSD(T)/cc-pVTZ) = -229.022972E(CCSD(T)/cc-pVQZ) = -229.084362

ABC

63.31036.71100.0

28.51550 1.74089 1.64072

CCCCCCHH

2.043489-0.830588-1.859418-0.805769 0.000000 1.075553 2.894148-0.633744

2.099810-2.198034-1.314772-0.416242 0.572506 1.345675 2.736527-3.270184

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

736i, 83, 156, 368, 370, 372, 466, 532, 587, 684, 695, 856, 1289, 1412, 1930, 2036, 3104, 3465

1i1(C2v),1A1

ZPE(B3LYP/6-311G**) = 0.046392E(B3LYP/6-311G**) = -229.553973E(CCSD(T)/cc-pVDZ) = -228.865832E(CCSD(T)/cc-pVTZ) = -229.071607E(CCSD(T)/cc-pVQZ) = -229.133769

ABC

103.8 589.0594.5

17.39071 3.06391 3.03594

CCCCCHCH

-0.757475 0.000000

0.757475 0.000000 0.000000 0.000000 0.000000 0.000000

0.000000 0.000000 0.000000 0.000000 0.652759 1.584968-0.652759-1.584968

0.992226 2.182603 0.992226-0.281042-1.588336-2.128025-1.588336-2.128025

236, 364, 396, 537, 558, 657, 719, 899, 912, 937, 954, 1026, 1068, 1369, 1483, 1707, 3250, 3293

1i2(C2v),1A1

ZPE(B3LYP/6-311G**) = 0.045766E(B3LYP/6-311G**) = -229.563650E(CCSD(T)/cc-pVDZ) = -228.859881E(CCSD(T)/cc-pVTZ) = -229.069071E(CCSD(T)/cc-pVQZ) = -229.132007

ABC

95.7759.1774.3

18.86269 2.37736 2.33079

CCCCCHCH

0.685333-0.685333 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000

0.000000 0.000000 0.000000 0.000000 0.658324 1.593591-0.658324-1.593591

2.057239 2.057239 0.800115-0.531404-1.802213-2.336287-1.802213-2.336287

137, 181, 228, 451, 563, 597, 710, 842, 902, 929, 944, 1055, 1184, 1360, 1611, 1834, 3258, 3302

1i3(C1),1A

ZPE(B3LYP/6-311G**) = 0.046569E(B3LYP/6-311G**) = -229.554224E(CCSD(T)/cc-pVDZ) = -228.859339E(CCSD(T)/cc-pVTZ) = -229.063673E(CCSD(T)/cc-pVQZ) = -229.124937

ABC

104.0691.9763.5

17.35681 2.60851 2.36391

CCCCCHCH

1.486901 2.754140-0.959115 0.169622-1.825803-2.806991-0.963467-1.166676

-0.016346-0.021161-0.976489-0.003084-0.138094-0.219010 0.896864 1.768867

0.022968 0.161058-0.357170-0.118673 0.347666 0.789593-0.072303-0.690874

137, 164, 311, 477, 537, 669, 704, 768, 870, 978, 1054, 1159, 1276, 1404, 1474, 2069, 3135, 3255

1i4(C2v),1A1

ZPE(B3LYP/6-311G**) = 0.046103E(B3LYP/6-311G**) = -229.5895535E(CCSD(T)/cc-pVDZ) = -228.878815E(CCSD(T)/cc-pVTZ) = -229.089192E(CCSD(T)/cc-pVQZ) = -229.150802

ABC

54.71005.41060.1

33.0076 1.79503 1.70245

CHCCCHCC

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

0.650852 1.597574-0.650852 0.000000 0.000000-1.597574 0.000000 0.000000

-2.018694-2.531089-2.018694-0.712966 0.573523-2.531089 1.868431 3.152097

115, 147, 258, 327, 420, 585, 631, 667, 846, 858, 956, 1018, 1210, 1636, 1865, 2130, 3260, 3309

1i5(C2v),1A1

ZPE(B3LYP/6-311G**) = 0.049280E(B3LYP/6-311G**) = -229.619818E(CCSD(T)/cc-pVDZ) = -228.928556E(CCSD(T)/cc-pVTZ) = -229.138142

ABC

248.6 259.9508.5

7.25842 6.94471 3.54905

CCCC

0.0000000.0000000.0000000.000000

0.721735-0.721735-1.348105-0.660788

1.068505 1.068505-0.171262-1.235019

89, 239, 491, 528, 551, 722, 755, 916, 1014, 1107, 1166, 1226, 1371, 1441, 1718, 1896, 3193, 3209

E(CCSD(T)/cc-pVQZ) = -229.201587 CCHH

0.0000000.0000000.0000000.000000

0.660788 1.348105 1.225711-1.225711

-1.235019-0.171262 2.026658 2.026658

1i6(Dv),1g

+

ZPE(B3LYP/6-311G**) = 0.047689E(B3LYP/6-311G**) = -229.705401E(CCSD(T)/cc-pVDZ) = -228.989247 E(CCSD(T)/cc-pVTZ) = -229.206810 E(CCSD(T)/cc-pVQZ) = -229.268695

ABC

0.01354.81354.8

91046.57 1.33202 1.33200

CCCCCCHH

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

3.173578-3.173578-1.964404-0.608633 0.608633 1.964404 4.236060-4.236060

114, 114, 278, 278, 487, 487, 571, 571, 636, 650, 650, 651, 651, 1209, 2106, 2221, 2308, 3474, 3475

1i7(Cs),1A’

ZPE(B3LYP/6-311G**) = 0.046271E(B3LYP/6-311G**) = -229.527846E(CCSD(T)/cc-pVDZ) = -228.830360E(CCSD(T)/cc-pVTZ) = -229.035886E(CCSD(T)/cc-pVQZ) = -229.096453

ABC

95.4752.6835.6

18.91667 2.39790 2.15993

CCCCCHCH

-0.067133-0.181741 0.811871 0.000000 0.750470-1.352506-0.862632-1.352506

1.530845 2.803718-0.906907 0.212109-2.194768-1.274794-1.020066-1.274794

0.000000 0.000000 0.000000 0.000000 0.000000 0.931242 0.000000-0.931242

122, 135, 221, 224, 496, 498, 588, 859, 920, 969, 1022, 1047, 1450, 1472, 1831, 2078, 3130, 3249

1i8(Cs),1A’

ZPE(B3LYP/6-311G**) = 0.045227E(B3LYP/6-311G**) = -229.544138E(CCSD(T)/cc-pVDZ) = -228.835016E(CCSD(T)/cc-pVTZ) = -229.040967E(CCSD(T)/cc-pVQZ) = -229.101359

ABC

68.7970.8

1027.2

26.28242 1.85901 1.75688

CCCCCHCH

-0.566757-1.122092 0.501648 0.000000 1.380636-0.498857-0.027149-0.498857

1.730075 2.887254-0.610415 0.574331-1.680890-2.431102-2.089988-2.431102

0.000000 0.000000 0.000000 0.000000 0.000000 0.921792 0.000000-0.921792

111, 122, 249, 252, 524, 554, 567, 748, 761, 946, 960, 1085, 1314, 1450, 1854, 2160, 3057, 3139

1i9(C2v),1A1

ZPE(B3LYP/6-311G**) = 0.046179E(B3LYP/6-311G**) = -229.532634E(CCSD(T)/cc-pVDZ) = -228.826259 E(CCSD(T)/cc-pVTZ) = -229.035356E(CCSD(T)/cc-pVQZ) = -229.098340

ABC

247.4280.1516.6

7.29467 6.44360 3.49368

CCCHCCCH

0.000000 0.000000 0.000000 0.870724 0.000000 0.000000 0.000000-0.870724

1.010543 1.342319 0.000000 0.000000-1.010543 0.000000-1.342319 0.000000

0.716202-0.521292 1.577405-1.975453 0.716202-1.308740-0.521292-1.975453

200, 323, 416, 468, 538, 553, 721, 728, 833, 1123, 1128, 1239, 1302, 1331, 1543, 1716, 3035, 3071

1i10(C2v),1A1

ZPE(B3LYP/6-311G**) = 0.045917E(B3LYP/6-311G**) = -229.530694E(CCSD(T)/cc-pVDZ) = -228.850704 E(CCSD(T)/cc-pVTZ) = -229.054345E(CCSD(T)/cc-pVQZ) = -229.115958

ABC

248.2281.3 518.3

7.27097 6.41610 3.48207

CCCHCCCH

0.000000 0.000000 0.000000-0.882004 0.000000 0.000000 0.000000 0.882004

1.341869 1.189969 0.000000 0.000000-1.341869 0.000000-1.189969 0.000000

-0.896939 0.440306-1.097092 1.993744-0.896939 1.345777 0.440306 1.993744

273, 332, 463, 514, 522, 633, 669, 728, 901, 960, 1130, 1138, 1182, 1342, 1555, 1652, 3063, 3100

1i11(C2v),1A1

ZPE(B3LYP/6-311G**) = 0.045994E(B3LYP/6-311G**) = -229.636713E(CCSD(T)/cc-pVTZ) = -228.917450 E(CCSD(T)/cc-pVTZ) = -229.127920E(CCSD(T)/cc-pVTZ) = -229.188600

ABC

6.21335.81342.0

289.4303 1.35108 1.34480

CHCCCHCC

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

0.000000 0.930741 0.000000 0.000000 0.000000-0.930741 0.000000 0.000000

-1.714485-3.579142-3.020730-0.436820 0.832231-3.579142 2.125135 3.407716

97, 107, 218, 243, 387, 480, 561, 611, 657, 809, 965, 1219, 1412, 1772, 2108, 2211, 3126, 3206

1TS1(Cs),1A’

ZPE(B3LYP/6-311G**) = 0.045437E(B3LYP/6-311G**) = -229.542978E(CCSD(T)/cc-pVDZ) = -228.848898 E(CCSD(T)/cc-pVTZ) = -229.056437

ABC

106.3636.9641.0

16.97878 2.83362 2.81545

CCCC

0.069608-0.938532 0.565670 0.156945

-2.219470-1.232607-0.929715 0.369190

0.000000 0.000000 0.000000 0.000000

349i, 217, 304, 320, 542, 699, 713, 811, 908, 953, 956, 1079, 1100, 1393, 1602, 1793, 3256, 3299

E(CCSD(T)/cc-pVQZ) = -229.118650 CHCH

0.069608 0.021275 0.069608 0.021275

1.643236 2.178391 1.643236 2.178391

0.656994 1.590442-0.656994-1.590442

1TS2(C1),1A

ZPE(B3LYP/6-311G**) = 0.043165E(B3LYP/6-311G**) = -229.474071E(CCSD(T)/cc-pVDZ) = -228.782056 E(CCSD(T)/cc-pVTZ) = -228.988527E(CCSD(T)/cc-pVQZ) = -229.050146

ABC

137.4545.9588.8

13.13181 3.30610 3.06534

CCCCCHCH

1.107292 2.276926 0.395119-0.188605-1.351261-1.470997-1.609766-2.307232

-0.510755-0.015815 0.810727-0.374322 0.634302 1.403364-0.549566-1.370795

-0.194810-0.343926 0.735962 0.370909-0.418163-1.161376 0.041242 0.014090

353i, 77, 190, 346, 419, 432, 574, 601, 794, 831, 862, 1045, 1189, 1461, 1671, 1899, 3249, 3306

1TS3(C1),1A

ZPE(B3LYP/6-311G**) = 0.044593E(B3LYP/6-311G**) = -229.543029E(CCSD(T)/cc-pVDZ) = -228.838808 E(CCSD(T)/cc-pVTZ) = -229.048401E(CCSD(T)/cc-pVQZ) = -229.110734

ABC

95.8787.8840.0

18.82957 2.29082 2.14847

CCCCCHCH

-2.252613-2.055146-0.724271 0.552243 1.785550 2.193543 1.911155 2.504948

0.553325-0.426241-0.240156-0.091988 0.694566 1.662694-0.538228-1.370351

0.487963-0.358359-0.167654-0.081556-0.150722-0.383451 0.238492 0.574472

494i, 154, 205, 240, 318, 563, 647, 703, 822, 845, 962, 1012, 1290, 1584, 1667, 1986, 3263, 3313

1TS4(C1),1A

ZPE(B3LYP/6-311G**) = 0.040717E(B3LYP/6-311G**) = -229.493188E(CCSD(T)/cc-pVDZ) = -228.794791E(CCSD(T)/cc-pVTZ) = -229.003686E(CCSD(T)/cc-pVQZ) = -229.066407

ABC

143.9505.8649.7

12.53809 3.56837 2.77780

CCCCCHCH

0.512136 1.790259 1.640752-0.741984-1.878747-2.947023-0.906824 0.453470

-0.866621-0.403885 0.850730-0.815947 0.069625-0.070586 0.935355 1.455039

-0.000018 0.000121-0.000056-0.000131 0.000089 0.000191-0.000048 0.000063

1466i, 189, 279, 343, 358, 382, 512, 545, 758, 869, 877, 1087, 1275, 1579, 1688, 1868, 2002, 3261

1TS5(C1),1A

ZPE(B3LYP/6-311G**) = 0.043778E(B3LYP/6-311G**) = -229.464349E(CCSD(T)/cc-pVDZ) = -228.779281E(CCSD(T)/cc-pVTZ) = -228.984307E(CCSD(T)/cc-pVQZ) = -229.046471

ABC

176.9 346.2425.6

10.20373 5.21324 4.24008

CCCCCHCH

1.367512 1.280065 0.271258 0.011994-1.017586-1.273440-1.349078-2.111549

-0.715509 0.526391 0.685886-0.714571 0.740948 1.572747-0.581247-1.224132

-0.084104-0.567722 0.790401 0.304946-0.100424-0.746313-0.129493-0.535312

483i, 245, 402, 472, 511, 600, 630, 783, 818, 874, 945, 1093, 1161, 1350, 1376, 1490, 3196, 3271

1TS6(C1),1A

ZPE(B3LYP/6-311G**) = 0.041334E(B3LYP/6-311G**) = -229.458820E(CCSD(T)/cc-pVDZ) = -228.765647E(CCSD(T)/cc-pVTZ) = -228.969367E(CCSD(T)/cc-pVQZ) = -229.030287

ABC

104.4709.6775.6

17.28134 2.54327 2.32682

CCCCCHCH

-1.494536-2.762857 0.975627-0.183119 1.974129 2.036846 0.941155 1.260757

-0.017669-0.089590-0.815851 0.072177-0.451804 0.638901 0.932115 1.584827

-0.023296-0.143954 0.407699 0.103355-0.360699-0.873431 0.023880 0.831514

1330i, 131, 163, 274, 461, 541, 584, 595, 753, 873, 957, 990, 1136, 1499, 1572, 2081, 2382, 3150

1TS7(Cs),1A’

ZPE(B3LYP/6-311G**) = 0.045750E(B3LYP/6-311G**) = -229.577749E(CCSD(T)/cc-pVDZ) = -228.877744 E(CCSD(T)/cc-pVTZ) = -229.090982E(CCSD(T)/cc-pVQZ) = -229.154227

ABC

265.8317.1582.9

6.78900 5.69183 3.09617

CCCCCCHH

0.004677-0.004677-0.006667 0.006667-0.006667 0.006667-0.004057 0.004057

-1.100269 1.100269 1.387285 0.626482-0.626482-1.387285-1.430450 1.430450

1.069087 1.069087-0.161659-1.255416-1.255416-0.161659 2.087931 2.087931

433i, 150, 261, 388, 492, 493, 576, 640, 668, 780, 873, 1176, 1342, 1727, 1875, 1931, 3354, 3355

1TS8(C1),1A

ZPE(B3LYP/6-311G**) = 0.045521E(B3LYP/6-311G**) = -229.521723E(CCSD(T)/cc-pVDZ) = -228.821102E(CCSD(T)/cc-pVTZ) = -229.027565

ABC

85.5775.6848.5

21.11397 2.32696 2.12701

CCCC

-1.575948-2.839183 0.938368-0.277452

-0.101548 0.099522-0.751877-0.230500

-0.000102 0.000176-0.000079-0.000066

389i, 125, 149, 239, 411, 568, 607, 785, 968, 975, 1016, 1036, 1411, 1474, 1760, 2105, 3115, 3240

E(CCSD(T)/cc-pVQZ) = -229.088286 CHCH

2.206278 1.137434 1.168799 1.137393

-0.358204 1.417469 0.870142 1.417323

-0.000001-0.934232 0.000043 0.934402

1TS9(C1),1A

ZPE(B3LYP/6-311G**) = 0.044233E(B3LYP/6-311G**) = -229.534751E(CCSD(T)/cc-pVDZ) = -228.823772E(CCSD(T)/cc-pVTZ) = -229.031401E(CCSD(T)/cc-pVQZ) = -229.092203

ABC

69.21032.31089.1

26.07418 1.74824 1.65706

CCCCCHCH

1.880955 3.143068-0.641278 0.601661-1.962788-2.379975-2.228348-2.379649

0.027526 0.261305-0.467241-0.186928-0.696705 1.210539 0.658490 1.210776

-0.000089 0.000202 0.000440-0.000473-0.000108 0.928687 0.000010-0.928582

532i, 129, 130, 270, 285, 444, 479, 575, 755, 933, 1086, 1238, 1372, 1473, 1901, 2115, 3070, 3163

1TS10(C1),1A

ZPE(B3LYP/6-311G**) = 0.044280 E(B3LYP/6-311G**) = -229.509885E(CCSD(T)/cc-pVDZ) = -228.808693E(CCSD(T)/cc-pVTZ) = -229.018358E(CCSD(T)/cc-pVQZ) = -229.081729

ABC

234.1274.4500.6

7.70969 6.57690 3.60487

CCCHCCCH

0.764425-0.455091 1.569627-2.354384 0.647435-1.278121-0.653289-1.215535

0.960942 1.343392-0.105160 0.182023-1.013325 0.132971-1.246162-0.617973

0.000231-0.012052 0.019346-0.168425-0.015089-0.036622-0.091286 0.981259

1091i, 376, 440, 490, 550, 566, 651, 782, 859, 1019, 1163, 1226, 1317, 1350, 1570, 1783, 2130, 3166

1TS11(Cs),1A’

ZPE(B3LYP/6-311G**) = 0.044822E(B3LYP/6-311G**) = -229.522181E(CCSD(T)/cc-pVDZ) = -228.829257 E(CCSD(T)/cc-pVTZ) = -229.036061E(CCSD(T)/cc-pVQZ) = -229.098971

ABC

262.0270.2521.3

6.88712 6.68025 3.46214

CCCHCCCH

-1.178652-1.303542-0.000001 0.000001 1.178651 0.000000 1.303544 0.000001

-0.809663 0.500778-1.350032 1.976505-0.809665 1.308968 0.500779 1.976505

0.000000 0.000000 0.000000 0.871258 0.000000 0.000000 0.000000-0.871258

466i, 206, 246, 440, 485, 639, 648, 672, 850, 1106, 1109, 1207, 1245, 1308, 1688, 1721, 3038, 3068

1TS12(C1),1A

ZPE(B3LYP/6-311G**) = 0.044429 E(B3LYP/6-311G**) = -229.515555E(CCSD(T)/cc-pVDZ) = -228.812750E(CCSD(T)/cc-pVTZ) = -229.021511E(CCSD(T)/cc-pVQZ) = -229.083999

ABC

269.4 312.6 570.1

6.70011 5.77283 3.16589

CCCHCCCH

0.197983 1.263322-1.055705 1.508558-1.336695 1.222189-0.794146 1.509751

-1.337859-0.632451-0.985408 1.287641 0.289766 0.763294 1.473280 1.288632

0.000271 0.000197-0.000340-0.910964-0.000002-0.000203 0.000310 0.909572

406i, 149, 239, 288, 386, 460, 556, 581, 899, 979, 1095, 1221, 1382, 1529, 1636, 1831, 3100, 3173

1TS13(Cs),1A’

ZPE(B3LYP/6-311G**) = 0.035526 E(B3LYP/6-311G**) = -229.471022E(CCSD(T)/cc-pVDZ) = -228.758110 E(CCSD(T)/cc-pVTZ) = -228.963372 E(CCSD(T)/cc-pVQZ) = -229.023003

ABC

23.21349.21372.3

77.91961 1.33766 1.31508

CHCCCHCC

0.157618 2.381814 0.045042 0.000000-0.148158 1.674358-0.292755-0.437775

1.710307 3.450112 3.006434 0.431118-0.832239 3.750087-2.114473-3.401180

0.0000000.0000000.0000000.0000000.0000000.0000000.0000000.000000

247i, 90, 107, 172, 233, 275, 391, 398, 436, 478, 572, 625, 695, 1237, 1741, 2033, 2168, 3944

1TS14(Cs),1A’

ZPE(B3LYP/6-311G**) = 0.041574 E(B3LYP/6-311G**) = -229.463015E(CCSD(T)/cc-pVDZ) = -228.756255E(CCSD(T)/cc-pVTZ) = -228.967240E(CCSD(T)/cc-pVQZ) = -229.031635

ABC

218.9278.1494.7

8.24481 6.48996 3.64845

CCCHCCCH

0.000001 0.000001-0.000222 0.401479 0.000001 0.000103 0.000001-0.400789

-0.709413 0.559859-1.620000 2.532813-0.709413 1.074816 0.559859 2.532934

0.957876 1.273964 0.000000 0.000000-0.957876 0.000000-1.273964 0.000000

934i, 351, 484, 502, 557, 578, 640, 643, 703, 775, 1094, 1121, 1246, 1266, 1364, 1570, 1762, 3594

Figure S1. Equilibrium geometries of the low-energy structural isomers of the C4 molecule. Bond lengths (Å)

and bond angles (degrees) were calculated at B3LYP/6-311G(d,p) level.

Figure S2. Geometric structures of C6H2 intermediates and C6H products of the l-C4 ( g3 ) + C2H2 reaction

optimized at the B3LYP/6-311G(d,p) level. Bond lengths are given angstrom and bond angles in degrees.

Figure S3. Geometric structures of transition states on the C6H2 potential energy surface involved in the l-C4

( g3 ) + C2H2 reaction optimized at the B3LYP/6-311G(d,p) level. Bond lengths are given angstrom and

bond angles in degrees.

Figure S4. Geometric structures of C6H2 intermediates and C6H products of the r-C4 ( gA1 ) + C2H2 reaction

optimized at the B3LYP/6-311G(d,p) level. Bond lengths are given angstrom and bond angles in degrees.

Figure S5. Geometric structures of transition states on the C6H2 potential energy surface involved in the r-C4

( gA1 ) + C2H2 reaction optimized at the B3LYP/6-311G(d,p) level. Bond lengths are given angstrom and

bond angles in degrees.