============================================================================= "Spectroscopic and Computational Studies on the Rearrangement of Ionized [1.1.1]Propellane and Some of its Valence Isomers: The Key Role of Vibronic Coupling" ============================================================================= by B. Muller, T. Bally,* R. Pappas and F. Williams SUPPORTING INFORMATION ********************** Complete Reference 37 (Gaussian Program): M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople, Gaussian 03, Rev E.01, Gaussian, Inc., Wallingford CT, 2004. Energies and geometries of all stationary points located and characterized in the course of the above study results of vibrational calculations (zero-point and thermal corrections) are from B3LYP/6-31G* calculations. -------------------------------------------------------------------------- [1.1.1]Propellane neutral (1), D3h symmetry -------------------------------------------------------------------------- B3LYP/6-31G* energy: -194.0089767 RCCSD(T)/cc-pVTZ energy -193.2932840 nuclear repulsion energy 163.4541056 Hartrees Zero-point correction= 0.093860 Thermal correction to Energy= 0.097801 Thermal correction to Enthalpy= 0.098746 Thermal correction to Gibbs Free Energy= 0.069260 Sum of electronic and zero-point Energies= -193.915117 Low frequencies --- -0.0094 -0.0063 -0.0061 10.4338 10.5030 19.1146 Low frequencies --- 536.4157 536.4178 620.0884 6 0.000000 0.000000 0.789662 6 0.000000 0.000000 -0.789662 6 0.000000 1.297001 0.000000 6 -1.123236 -0.648501 0.000000 6 1.123236 -0.648501 0.000000 1 0.915402 1.884836 0.000000 1 -0.915402 1.884836 0.000000 1 -2.090017 -0.149656 0.000000 1 -1.174615 -1.735180 0.000000 1 1.174615 -1.735180 0.000000 1 2.090017 -0.149656 0.000000 -------------------------------------------------------------------------- [1.1.1]Propellane radical cation (1.+), D3h symmetry -------------------------------------------------------------------------- B3LYP/6-31G* energy: -193.6640079 (S**2=0.767529) RCCSD(T)/cc-pVTZ energy nuclear repulsion energy 162.5518596423 Hartrees Zero-point correction= 0.090968 Thermal correction to Energy= 0.094704 Thermal correction to Enthalpy= 0.095648 Thermal correction to Gibbs Free Energy= 0.065749 Sum of electronic and zero-point Energies= -193.573040 Low frequencies --- -205.1650 -205.0373 -0.0455 -0.0120 -0.0057 20.2899 Low frequencies --- 22.1487 22.2110 535.8496 6 0.000000 0.000000 0.772482 6 0.000000 0.000000 -0.772482 6 0.000000 1.320552 0.000000 6 -1.143631 -0.660276 0.000000 6 1.143631 -0.660276 0.000000 1 0.924877 1.892147 0.000000 1 -0.924877 1.892147 0.000000 1 -2.101086 -0.145106 0.000000 1 -1.176209 -1.747041 0.000000 1 1.176209 -1.747041 0.000000 1 2.101086 -0.145106 0.000000 -------------------------------------------------------------------------- [1.1.1]Propellane radical cation (1.+), Cs symmetry -------------------------------------------------------------------------- State=2-A' B3LYP/6-31G* energy: -193.6642372 (S**2=0.766164) RCCSD(T)/cc-pVTZ energy: -193.2934842 nuclear repulsion energy 162.0649975 Hartrees Zero-point correction= 0.091650 Thermal correction to Energy= 0.096616 Thermal correction to Enthalpy= 0.097560 Thermal correction to Gibbs Free Energy= 0.063643 Sum of electronic and zero-point Energies= -193.572587 Low frequencies --- -0.0006 0.0006 0.0009 24.3516 24.5389 34.9071 Low frequencies --- 146.2087 212.1905 517.5393 6 -0.019316 -0.776890 0.000000 6 0.000000 0.764023 0.000000 6 1.327639 0.154609 0.000000 6 -0.657641 -0.071974 1.151395 6 -0.657641 -0.071974 -1.151395 1 1.896520 0.121324 -0.925944 1 1.896520 0.121324 0.925944 1 -0.131905 -0.066666 2.102874 1 -1.743736 -0.048042 1.196898 1 -1.743736 -0.048042 -1.196898 1 -0.131905 -0.066666 -2.102874 -------------------------------------------------------------------------- [1.1.1]Propellane radical cation, transition state for rearrangement to methylenebicyclobutylidene radical cation (TS1) -------------------------------------------------------------------------- State=2-A' B3LYP/6-31G* energy: -193.6637344 (S**2=0.762087) RCCSD(T)/cc-pVTZ energy: -193.2920186 nuclear repulsion energy 160.5839220 Hartrees Zero-point correction= 0.091536 Thermal correction to Energy= 0.095607 Thermal correction to Enthalpy= 0.096552 Thermal correction to Gibbs Free Energy= 0.064422 Sum of electronic and zero-point Energies= -193.572199 Low frequencies --- -207.3726 -24.7256 -16.1547 -13.6357 0.0006 0.0006 Low frequencies --- 0.0007 434.9450 489.1167 ****** 1 imaginary frequencies (negative Signs) ****** 6 0.797093 -0.256725 0.000000 6 -0.690650 0.151662 0.000000 6 -0.028338 1.398609 0.000000 6 -0.028338 -0.662044 1.161900 6 -0.028338 -0.662044 -1.161900 1 0.144960 1.936286 -0.929300 1 0.144960 1.936286 0.929300 1 0.101753 -0.134630 2.103300 1 0.101753 -0.134630 -2.103300 1 -0.310999 -1.710031 1.235800 1 -0.310999 -1.710031 -1.235800 -------------------------------------------------------------------------- Methylenbicyclobutylidene radical cation (5.+), Cs symmetry -------------------------------------------------------------------------- State=2-A' B3LYP/6-31G* energy: -193.6820053 (S**2=0.755861) RCCSD(T)/cc-pVTZ energy: -193.3033420 nuclear repulsion energy 154.0506122 Hartrees Zero-point correction= 0.089278 Thermal correction to Energy= 0.094462 Thermal correction to Enthalpy= 0.095406 Thermal correction to Gibbs Free Energy= 0.061126 Sum of electronic and zero-point Energies= -193.592727 Low frequencies --- -13.3059 0.0007 0.0009 0.0015 11.9838 17.4938 Low frequencies --- 214.5484 234.8747 429.3965 6 0.191544 -1.202787 0.000000 6 0.000000 0.411753 0.000000 6 0.611344 1.612188 0.000000 6 -0.345195 -0.567909 1.179358 6 -0.345195 -0.567909 -1.179358 1 0.820295 2.134129 -0.930225 1 0.820295 2.134129 0.930225 1 0.265542 -0.528499 2.080140 1 0.265542 -0.528499 -2.080140 1 -1.423329 -0.661641 1.356449 1 -1.423329 -0.661641 -1.356449 -------------------------------------------------------------------------- Methylenbicyclobutylidene radical cation (5.+), transition state for inver- sion of ring (TS2, C2v symmetry) -------------------------------------------------------------------------- State=2-A1 B3LYP/6-31G* energy: -193.6613462 (S**2=0.756726) RCCSD(T)/cc-pVTZ energy: -193.2798479 nuclear repulsion energy 151.3570727 Hartrees Zero-point correction= 0.085811 Thermal correction to Energy= 0.090502 Thermal correction to Enthalpy= 0.091446 Thermal correction to Gibbs Free Energy= 0.058712 Sum of electronic and zero-point Energies= -193.575535 Low frequencies --- -87.4521 -8.7443 -5.9592 -0.0009 -0.0005 -0.0004 Low frequencies --- 12.3524 321.0426 347.0737 ****** 1 imaginary frequencies (negative Signs) ****** 6 0.000000 1.112923 -0.573860 6 0.000000 -1.112923 -0.573860 6 0.000000 0.000000 0.495459 6 0.000000 0.000000 -1.518571 6 0.000000 0.000000 1.822150 1 0.883161 1.771790 -0.668416 1 -0.883161 1.771790 -0.668416 1 0.883161 -1.771790 -0.668416 1 -0.883161 -1.771790 -0.668416 1 0.000000 0.929913 2.382875 1 0.000000 -0.929913 2.382875 -------------------------------------------------------------------------- Methylenbicyclobutylidene radical cation (5.+), transition state for decay to methylenecyclobutene radical cation by H-shift (TS3) -------------------------------------------------------------------------- B3LYP/6-31G* energy: -193.6780093 (S**2=0.769056) RCCSD(T)/cc-pVTZ energy: -193.2777323 nuclear repulsion energy 151.3559245 Hartrees Zero-point correction= 0.087403 Thermal correction to Energy= 0.092506 Thermal correction to Enthalpy= 0.093450 Thermal correction to Gibbs Free Energy= 0.059258 Sum of electronic and zero-point Energies= -193.590607 Low frequencies --- -263.9612 -14.2971 -0.0007 0.0001 0.0009 7.5133 Low frequencies --- 12.4869 254.5079 299.7364 ****** 1 imaginary frequencies (negative Signs) ****** 6 0.471099 1.317760 0.124218 6 -0.491688 0.189257 -0.042645 6 0.956716 0.053538 -0.479930 6 -1.733337 -0.303016 0.015820 6 1.009301 -1.161390 0.146658 1 0.795972 1.594322 1.131412 1 0.358442 2.144313 -0.576555 1 -2.555933 0.364705 0.262785 1 -1.968680 -1.341619 -0.192803 1 1.247381 -1.259001 1.210015 1 0.850271 -2.079619 -0.419575 -------------------------------------------------------------------------- Methylenbicyclobutylidene radical cation (5.+), transition state for decay To dimethylenecyclopropane radical cation (TS4) -------------------------------------------------------------------------- B3LYP/6-31G* energy: -193.6780093 (S**2=0.769056) RCCSD(T)/cc-pVTZ energy: -193.2968755 nuclear repulsion energy 151.3559245 Hartrees. Zero-point correction= 0.087403 Thermal correction to Energy= 0.092506 Thermal correction to Enthalpy= 0.093450 Thermal correction to Gibbs Free Energy= 0.059258 Sum of electronic and zero-point Energies= -193.590607 Low frequencies --- -263.9612 -14.2971 -0.0007 0.0001 0.0009 7.5133 Low frequencies --- 12.4869 254.5079 299.7364 ****** 1 imaginary frequencies (negative Signs) ****** 6 0.471099 1.317760 0.124218 6 -0.491688 0.189257 -0.042645 6 0.956716 0.053538 -0.479930 6 -1.733337 -0.303016 0.015820 6 1.009301 -1.161390 0.146658 1 0.795972 1.594322 1.131412 1 0.358442 2.144313 -0.576555 1 -2.555933 0.364705 0.262785 1 -1.968680 -1.341619 -0.192803 1 1.247381 -1.259001 1.210015 1 0.850271 -2.079619 -0.419575 ---------------------------------------------------------------------------- Dimethylenecyclopropane neutral (2), C2v symmetry ---------------------------------------------------------------------------- State=1-A1 B3LYP/6-31G* energy: -194.0354207 RCCSD(T)/cc-pVTZ energy nuclear repulsion energy 146.9152953 Hartrees Zero-point correction= 0.089934 Thermal correction to Energy= 0.095117 Thermal correction to Enthalpy= 0.096062 Thermal correction to Gibbs Free Energy= 0.062891 Sum of electronic and zero-point Energies= -193.945486 Low frequencies --- -7.1083 -4.3262 -0.0034 -0.0006 0.0013 8.3210 Low frequencies --- 236.3609 255.0486 343.4995 6 0.000000 0.000000 1.309659 6 0.000000 0.709415 -0.011392 6 0.000000 -0.709415 -0.011392 6 0.000000 1.873406 -0.652593 6 0.000000 -1.873406 -0.652593 1 -0.913496 0.000000 1.908610 1 0.913496 0.000000 1.908610 1 0.000000 1.921481 -1.738859 1 0.000000 2.817983 -0.114822 1 0.000000 -1.921481 -1.738859 1 0.000000 -2.817983 -0.114822 ---------------------------------------------------------------------------- Dimethylenecyclopropane radical cation (2.+), C2v symmetry (=TS!) ---------------------------------------------------------------------------- State=2-A2 B3LYP/6-31G* energy: -193.7198543 (S**2=0.783415) RCCSD(T)/cc-pVTZ energy: -193.3291352 nuclear repulsion energy 146.0634786 Hartrees Zero-point correction= 0.087710 Thermal correction to Energy= 0.093028 Thermal correction to Enthalpy= 0.093972 Thermal correction to Gibbs Free Energy= 0.059679 Sum of electronic and zero-point Energies= -193.632145 Low frequencies --- -62.0081 -1.1839 -0.0028 0.0014 0.0157 4.6416 Low frequencies --- 7.0237 153.7803 227.1597 6 0.000000 0.000000 1.357903 6 0.000000 0.688242 0.028776 6 0.000000 -0.688242 0.028776 6 0.000000 1.855267 -0.700554 6 0.000000 -1.855267 -0.700554 1 -0.917167 0.000000 1.950659 1 0.917167 0.000000 1.950659 1 0.000000 1.833972 -1.787998 1 0.000000 2.823319 -0.205697 1 0.000000 -1.833972 -1.787998 1 0.000000 -2.823319 -0.205697 ---------------------------------------------------------------------------- Dimethylenecyclopropane radical cation (2.+), C2 symmetry (=minimum) ---------------------------------------------------------------------------- State=2-A B3LYP/6-31G* energy: -193.7198578 (S**2=0.783207) RCCSD(T)/cc-pVTZ energy: -193.3291376 nuclear repulsion energy 146.0782945 Hartrees Zero-point correction= 0.087855 Thermal correction to Energy= 0.093936 Thermal correction to Enthalpy= 0.094880 Thermal correction to Gibbs Free Energy= 0.058794 Sum of electronic and zero-point Energies= -193.632003 Low frequencies --- -5.3997 -0.0246 -0.0034 -0.0003 0.5778 6.1730 Low frequencies --- 84.1907 154.8471 226.6336 6 0.000000 0.000000 1.357570 6 0.000000 0.688538 0.028479 6 0.000000 -0.688538 0.028479 6 -0.028599 1.854809 -0.700171 6 0.028599 -1.854809 -0.700171 1 -0.917090 0.021791 1.950009 1 0.917090 -0.021791 1.950009 1 -0.112218 1.834156 -1.784435 1 0.033204 2.822384 -0.208134 1 0.112218 -1.834156 -1.784435 1 -0.033204 -2.822384 -0.208134 ---------------------------------------------------------------------------- Dimethylenecyclopropane radical cation (2.+), transition state for rotation around one exocyclic double bond (TS5, Cs symmetry) ---------------------------------------------------------------------------- State=2-A' B3LYP/6-31G* energy: -193.6835392 (S**2=0.7543) RCCSD(T)/cc-pVTZ energy: -193.2960066 nuclear repulsion energy 145.7711755 Hartrees Zero-point correction= 0.084372 Thermal correction to Energy= 0.090168 Thermal correction to Enthalpy= 0.091112 Thermal correction to Gibbs Free Energy= 0.055343 Sum of electronic and zero-point Energies= -193.599167 Low frequencies ----1816.1670 -7.9346 -0.0007 -0.0004 0.0007 7.8788 Low frequencies --- 12.9642 146.4911 220.2421 ****** 1 imaginary frequencies (negative Signs) ****** 6 1.357700 -0.001363 0.000000 6 0.000000 0.655170 0.000000 6 0.054624 -0.721778 0.000000 6 -0.717390 1.865759 0.000000 6 -0.700429 -1.846279 0.000000 1 1.951747 0.071724 0.917128 1 1.951747 0.071724 -0.917128 1 -0.918590 2.381875 0.938959 1 -0.918590 2.381875 -0.938959 1 -1.786414 -1.781193 0.000000 1 -0.246928 -2.835055 0.000000 ---------------------------------------------------------------------------- Dimethylenecyclopropane radical cation (2.+), transition state for rearrange- Ment to dimethyleneallene radical cation (3+.): TS6 ---------------------------------------------------------------------------- B3LYP/6-31G* energy: -193.7118187 (S**2=0.767732) RCCSD(T)/cc-pVTZ energy: -193.32482828 nuclear repulsion energy 145.1761119322 Hartrees Zero-point correction= 0.086740 Thermal correction to Energy= 0.092039 Thermal correction to Enthalpy= 0.092983 Thermal correction to Gibbs Free Energy= 0.058275 Sum of electronic and zero-point Energies= -193.625078 Low frequencies --- -308.4086 -11.3713 -0.0008 -0.0007 0.0005 1.8418 Low frequencies --- 6.7223 209.9531 258.0141 ****** 1 imaginary frequencies (negative Signs) ****** 6 -0.696170 -0.178793 -0.051838 6 0.650109 -0.002118 -0.190658 6 1.773452 -0.781335 0.071272 6 0.278185 1.369181 -0.010848 6 -1.967929 -0.480797 0.078482 1 -2.618281 0.040291 0.779402 1 -2.413257 -1.260028 -0.542808 1 2.749600 -0.317771 0.173422 1 -0.270037 1.915259 -0.772438 1 1.692815 -1.861885 0.128152 1 0.633283 1.927302 0.855812 -------------------------------------------------------------------------- Dimethylenallene radical cation (3.+), C2v symmetry -------------------------------------------------------------------------- State=2-A2 B3LYP/6-31G* energy: 193.7240918 (S**2=0.800595) RCCSD(T)/cc-pVTZ energy: -193.3368846 nuclear repulsion energy 142.0969066 Hartrees Zero-point correction= 0.086111 Thermal correction to Energy= 0.092114 Thermal correction to Enthalpy= 0.093058 Thermal correction to Gibbs Free Energy= 0.057703 Sum of electronic and zero-point Energies= -193.637981 Low frequencies --- -11.1826 -0.0057 -0.0050 0.0006 2.6893 5.5622 Low frequencies --- 178.8216 232.4592 268.8316 6 0.000000 0.000000 0.841735 6 0.000000 0.000000 -0.543365 6 0.000000 1.268092 -1.181493 6 0.000000 -1.268092 -1.181493 6 0.000000 0.000000 2.123135 1 -0.935796 0.000000 2.689232 1 0.935796 0.000000 2.689232 1 0.000000 1.342394 -2.264647 1 0.000000 -1.342394 -2.264647 1 0.000000 2.182661 -0.600142 1 0.000000 -2.182661 -0.600142 -------------------------------------------------------------------------- f