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78149446238
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note
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12) = 3 × 10 -3 (mol/L)-1 s-1. 9
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14
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78149435275
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note
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n XOO •, are also known to have magnetically inequivalent 17 O atoms, 1 including X = N, O, F, P, S, As, Mn, Co, and Cu. Presumably, all these radicals have more or less the same linear, nonfluctional, structure as alkylperoxyls. They will not be considered further in this paper.
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15
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78149450022
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note
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3COO • are 4.6 and 0.8 (mol/L)-1 s-1 and 8.9 and 4.7 kcal/mol,respectively. 11
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16
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78149456342
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note
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Structures were optimized at the B3 17 P86 18 level of theory using 6-311+G(2d,2p) basis sets for C, H, O, Si, and Ge atoms. This approach has been shown to predict fairly accurate bond dissociation enthalpies in a broad range of compounds. 19 Small-core, averaged relativistic effective potentials (AREPs) and accompanying (uncontracted) basis sets were used for the Sn 20 and Pb 21 atoms. All calculations used the Gaussian 03 program package. 22
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17
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0000189651
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10.1063/1.464913
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Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, revision D.01; Gaussian, Inc.: Pittsburgh, PA, 2004.
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Honda, Y.28
Kitao, O.29
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Adamo, C.36
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Voth, G.A.47
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Rabuck, A.D.56
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Foresman, J.B.58
Ortiz, J.V.59
Cui, Q.60
Baboul, A.G.61
Clifford, S.62
Cioslowski, J.63
Stefanov, B.B.64
Liu, G.65
Liashenko, A.66
Piskorz, P.67
Komaromi, I.68
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more..
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23
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78149417157
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All "side-on" structures were found to have a single imaginary vibration frequency. Displacement along this vibration mode generates structures that have "end-on" character
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All "side-on" structures were found to have a single imaginary vibration frequency. Displacement along this vibration mode generates structures that have "end-on" character.
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24
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78149440876
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The general trend in E as a function of group-14 atomic mass was verified by performing QCISD(T) single-point energy calculations
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The general trend in E as a function of group-14 atomic mass was verified by performing QCISD(T) single-point energy calculations.
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25
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78149425574
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5OO •). As in the case of the 1,1-diphenylethoxyl radical 26, 27 and triphenylmethoxyl radical, 28 the phenylperoxyl radical is predicted to have a stable spiro-type intermediate that is 20.4 kcal/mol higher in energy than the open form of the radical. The barrier to the formation of the intermediate is predicted to be 26.9 kcal/mol
-
5OO •). As in the case of the 1,1-diphenylethoxyl radical 26, 27 and triphenylmethoxyl radical, 28 the phenylperoxyl radical is predicted to have a stable spiro-type intermediate that is 20.4 kcal/mol higher in energy than the open form of the radical. The barrier to the formation of the intermediate is predicted to be 26.9 kcal/mol.
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26
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