The C4H4·+ potential energy surface. 3. The reaction of acetylene with its radical cation

Journal of Physical Chemistry A

Volumn 101, Issue 21, 1997, Pages 3925-3935

  Hrouda, Vojtěch ^a,b   Roeselová, Martina ^a,b   Bally, Thomas ^a  

^a UNIVERSITY OF FRIBOURG   (Switzerland)

^b J HEYROVSKÝ INSTITUTE OF PHYSICAL CHEMISTRY   (Czech Republic)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001753796     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp964079z     Document Type: Article

References (64)

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33. Coupled cluster calculation accounting for single and double excitations (see e.g.: Bartlett, R. J. J. Phys. Chem. 1989, 93, 1697, and references cited therein), augmented by a quasi-perturbative estimate for triple excitations (Raghavachari, K.; Trucks, G. W.; Pople, J. A.; Head-Gordon, M. Chem. Phys. Lett. 1989, 157, 479).
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41. (c) Alberts, I. L.; Rowlands, T. W.; Handy, N. C. J. Chem. Phys. 1988, 89, 3811.
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43. Van der Waals systems: Hobza, P.; Sponer, J.; Reschel, T. J. Comput. Chem. 1995, 16, 1315. H-bonded complexes: Del Bene, J. E.; Person, W. B.; Szczepaniak, K. J. Phys. Chem. 1995, 99, 10705.
44. Handy, N. C.; Murray, Ch. W.; Amos, R. D. J. Phys. Chem. 1993, 97, 4392.
45. -1 which testifies to the flatness of the potential surface and the ease of automerization of TN.
46. See e.g.: Badger, B.; Brocklehurst, B. Trans. Faraday Soc. 1966, 66, 2939.
47. ·+: Hiraoka, K.; Fujimaki, S.; Aruga, K. J. Chem. Phys. 1991, 95, 8413, and references cited therein.
48. +.
49. +.
50. ·+! This must be due to the fact that the exchange parts of the functionals show a wrong asymptotic behavior, as shown recently by model calculations (Filippi, L.; Umrigar, C. J.; Taut, M. J. Chem. Phys. 1994, 100, 1290) or by calculations on charge transfer complexes (Ruiz, E.; Salahub, D. R.; Vela, A. J. Phys. Chem. 1996, 100, 12265).
51. ·+! This must be due to the fact that the exchange parts of the functionals show a wrong asymptotic behavior, as shown recently by model calculations (Filippi, L.; Umrigar, C. J.; Taut, M. J. Chem. Phys. 1994, 100, 1290) or by calculations on charge transfer complexes (Ruiz, E.; Salahub, D. R.; Vela, A. J. Phys. Chem. 1996, 100, 12265).
52. (a) CI with all singly and doubly excited configurations. In order to avoid possible problems with perturbative methods based on reference wavefunctions which may be far from the correlated ones, we preferred this fully variational procedure in this case.
53. (b) Note that the energy of PC relative to the separated fragments is strongly underestimated by CISD due to the size inconsistency of this procedure.
54. 2d symmetry (actually PC is a "degenerate" transition state for their pairwise automerization).
55. (a) Note that the bond lengths of LC1 (cf. Figure 6) are quite different from those reported in ref 16 for the corresponding structure 7(b). Whereas the long bond distance depends very strongly on the basis set (1.79 by 3-21G, 1.70 by 6-31G*) and is reduced by ≈0.05 Å by correlation, a recalculation of LC1 by UHF/3-21G showed that the short bond length given in ref 16 is too short by ≈0.1 Å.
56. (b) Booze and Baer reported their structure 7(b) (our LC1) to be an energy minimum at the UHF/3-21G level. We confirmed this but found that, on going to UHF/6-31G*, it turns into a transition state with an imaginary mode pointing toward CC to which it collapses spontaneously. By ROHF/6-31G* it remains a minimum which is, however, a meaningless result due to the instability of the ROHF wave function.
57. (c) Their structure 7e corresponds to the cis-conformation of LC2 which is a local minimum at the UHF/3-21G level.
58. Note that there are two possible conformations of CC. The one shown in Figure 9 has the H atom at the "carbenic" center facing the three-membered ring, whereas in another (nearly isoenergetic) one that H atom faces the opposite way. It is the first structure which is formed in the LC1-TS1-CC rearrangement, but both conformers of CC decay with similar activation energies to CB. At the B3LYP/6-31G* level, the rotational barrier for interconversion of the two conformers is 3.2 kcal/mol.
59. 2 symmetry leads via a second order saddle point (SP2 in Figure 8) and is therefore not competitive with the reaction via CC.
60. 298(MCP) = 280.4 kcal/mol.
61. Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. S.; Mallard, W. G. Gas Phase Ion and Neutral Thermochemistry; American Chemical Society: Washington, DC, 1988 (J. Phys. Chem. Ref. Data 1988, 17, Suppl. No. 1).
62. Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. S.; Mallard, W. G. Gas Phase Ion and Neutral Thermochemistry; American Chemical Society: Washington, DC, 1988 (J. Phys. Chem. Ref. Data 1988, 17, Suppl. No. 1).
63. Rodgers, D. W.; McLafferty, F. J.; Podosenin, A. V. J. Phys. Chem. 1996, 100, 17148.
64. 298(VA) on which the above numbers are based is too low.