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Analysis carried out using the CRUNCH program developed by P. B. Armentrout and K. M. Ervin
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Analysis carried out using the CRUNCH program developed by P. B. Armentrout and K. M. Ervin.
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65
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Bending frequencies were obtained by loosening the carbon-halide bending modes in the reactant anions by factors between 2 and 10. Threshold curves were fit with assumed transition states corresponding to activation entropies that were 2 eu higher and 2 eu lower than the ones used in the final analysis. The effect on the threshold energies was less than or equal to 1 kcal/mol for all three halobenzyl anion dissociations.
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66
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85005470381
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We employed an average scale factor of 0.9 because some of the calculated frequencies were analytically derived while others were numerically evaluated. This value is in the range of the one recommended by Pople and Radom for HF/6-31G* frequencies. Pople, J. A.; Scott, A. P.; Wong, M. W.; Radom, L. Isr. J. Chem. 1993, 33, 345.
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note
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The active orbital spaces for these calculations consisted of the nonbonding σ and π orbitals of each carbene. A single reference configuration was used for the triplet states (i.e., ROHF/6-31G*). and a two-configuration reference was used for each singlet state (i.e. TCSCF/6-31G*).
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Gaussian 92/DFT Revision G.3; Frisch, M. J.; Trucks, G. W.; Schlengel, H. B.; Gill, P. M. W.; Johnson, B. G.; Wong, M. W.; Foresman, J. B.; Robb, M. A.; Head-Gordon, M.; Replogle, E. S.; Gomperts, R.; Andres, J. L.; Raghavachari, K.; Binkley, J. S.; Gonzalez, C.; Martin, R. L., Fox, D. J.; Defrees, D. J.; Baker, J.; Stewart, J. J. P.; Pople, J. A.; Gaussian, Inc.: Pittsburgh, PA, 1993.
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Frisch, M.J.1
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The energy-resolved cross section obtained with argon target is similar in appearance, although it displays somewhat more tailing in the threshold region. Because of the greater spread in the lab-frame collision energies when neon compared to argon target is used, the former is preferred for energy-resolved analysis of low-dissociation energy reactions.
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83
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Translational and rotational contributions to the heat capacity are treated classically, and the vibrational components were obtained from calculated vibrational frequencies.
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Methyl chloride: Smith, B. J.; Radom, L. J. Phys. Chem. 1991, 95, 10549. Methyl bromide: Mayer, P. A.; Radom, L. Personal communication of unpublished results.
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The 1-bromoallyl anion was also generated by proton abstraction from 1-bromopropene; the behavior of bromoallyl ions produced from the two different precursors is identical.
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91
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1842358937
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The 1-halopropenes are 1-2 kcal/mol lower in energy than the 3-halopropene isomers (ref 5), which means that the 3-position in a 1-haloallyl anion is the thermodynamically preferred site of protonation.
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92
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A concise description of these calculations can be found in ref 56. Note that the first term of eq A2 in this paper contains a minor typographical error, it should read 5/2R ln(T).
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