Phenyl radical, cation, and anion. The triplet-singlet gap and higher excited states of the phenyl cation

Journal of the American Chemical Society

Volumn 119, Issue 34, 1997, Pages 8083-8088

  Nicolaides, Athanassios ^a,b   Smith, David M ^a   Jensen, Frank ^a,c   Radom, Leo ^a  

^a AUSTRALIAN NATIONAL UNIVERSITY   (Australia)

^b UNIVERSITY OF SOUTHERN DENMARK   (Denmark)

^c MIE UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

BENZENE; PHENYL GROUP; RADICAL;

ARTICLE; CHEMICAL BOND; CHEMICAL REACTION; DECOMPOSITION; ENERGY; IONIZATION; MASS SPECTROMETRY;

EID: 0030866326     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja970808s     Document Type: Article

References (70)

1. Waters, W. A. J. Chem. Soc. 1942, 266.
2. See, for example: Gasper, S. M.; Devadoss, C.; Schuster, G. B. J. Am. Chem. Soc. 1995, 117, 5206.
3. For reviews, see: (a) Zollinger, H. Acc. Chem. Res. 1973, 6, 335. (b) Chlebowski, J. F. In Carbonium Ions; Olah, G. A., Schleyer, P. v. R., Eds.; Wiley: New York, 1970: Vol. 2, p 700. (c) Richey, H. G., Jr.; Richey, J. M. ref 4b, Chapter 21.
4. For reviews, see: (a) Zollinger, H. Acc. Chem. Res. 1973, 6, 335. (b) Chlebowski, J. F. In Carbonium Ions; Olah, G. A., Schleyer, P. v. R., Eds.; Wiley: New York, 1970: Vol. 2, p 700. (c) Richey, H. G., Jr.; Richey, J. M. ref 4b, Chapter 21.
5. For reviews, see: (a) Zollinger, H. Acc. Chem. Res. 1973, 6, 335. (b) Chlebowski, J. F. In Carbonium Ions; Olah, G. A., Schleyer, P. v. R., Eds.; Wiley: New York, 1970: Vol. 2, p 700. (c) Richey, H. G., Jr.; Richey, J. M. ref 4b, Chapter 21.
6. (a) Swain, C. G.; Sheats, J. E.; Harbison, K. G. J. Am. Chem. Soc. 1975, 97, 783.
7. (b) Swain, C. G.; Sheats, J. E.; Gorenstein, D. G.; Harbison, K. G. J. Am. Chem. Soc. 1975, 97, 791.
8. (c) Swain, C. G.; Sheats, J. E.; Harbison, K. G. J. Am. Chem. Soc. 1975, 97, 796.
9. Zollinger, H. Angew. Chem., Int. Ed. Engl. 1978, 17, 141.
10. Taft, R. W. J. Am. Chem. Soc. 1961, 83, 3350.
11. Ambroz, H. B.; Kemp, T. J. Chem. Soc. Rev. 1979, 8, 353.
12. Speranza, M. Gazz. Chim. Ital. 1983, 113, 37.
13. Sergeev, Yu. L.; Akopyan, M. E.; Vilesov, F. I. Opt. Spek. 1972, 32, 230.
14. Blush, J. A.; Clauberg, H.; Kohn, D. W.; Minsek, D. W.; Zhang, X.; Chen, P. Acc. Chem. Res. 1992, 25, 385.
15. Dill, J. D.; Schleyer, P. v. R.; Binkley, J. S.; Seeger, R.; Pople, J. A.; Haselbach, E. J. Am. Chem. Soc. 1976, 98, 5428.
16. Butcher, V.; Costa, M. L.; Dyke, J. M.; Ellis, A. R.; Morris, A. Chem. Phys. 1987, 115, 261.
17. Bernardi, F.; Grandinetti, F.; Guarino, A.; Robb, M. A. Chem. Phys. Lett. 1988, 153, 309.
18. Krauss, M.; Roszak, S. J. Mol. Struct., Theochem. 1994, 310, 155.
19. See, for example: (a) Kühlewind, H.; Kiermeier, A.; Neusser, H. J. J. Chem. Phys. 1986, 85, 4427. (b) Lifshitz, C.; Louage, F.; Aviyente, V.; Song, K. J. Phys. Chem. 1991, 95, 9298. (c) Klippenstein, S. J.; Faulk, J. D.; Dunbar, R. C. J. Chem. Phys. 1993, 98, 243. (d) Osterheld, T. H.; Baer, T.; Brauman, J. I. J. Am. Chem. Soc. 1993 115, 6284. (e) Yim, Y. H.; Kim, M. S. J. Phys. Chem. 1994, 98, 5201.
20. See, for example: (a) Kühlewind, H.; Kiermeier, A.; Neusser, H. J. J. Chem. Phys. 1986, 85, 4427. (b) Lifshitz, C.; Louage, F.; Aviyente, V.; Song, K. J. Phys. Chem. 1991, 95, 9298. (c) Klippenstein, S. J.; Faulk, J. D.; Dunbar, R. C. J. Chem. Phys. 1993, 98, 243. (d) Osterheld, T. H.; Baer, T.; Brauman, J. I. J. Am. Chem. Soc. 1993 115, 6284. (e) Yim, Y. H.; Kim, M. S. J. Phys. Chem. 1994, 98, 5201.
21. See, for example: (a) Kühlewind, H.; Kiermeier, A.; Neusser, H. J. J. Chem. Phys. 1986, 85, 4427. (b) Lifshitz, C.; Louage, F.; Aviyente, V.; Song, K. J. Phys. Chem. 1991, 95, 9298. (c) Klippenstein, S. J.; Faulk, J. D.; Dunbar, R. C. J. Chem. Phys. 1993, 98, 243. (d) Osterheld, T. H.; Baer, T.; Brauman, J. I. J. Am. Chem. Soc. 1993 115, 6284. (e) Yim, Y. H.; Kim, M. S. J. Phys. Chem. 1994, 98, 5201.
22. See, for example: (a) Kühlewind, H.; Kiermeier, A.; Neusser, H. J. J. Chem. Phys. 1986, 85, 4427. (b) Lifshitz, C.; Louage, F.; Aviyente, V.; Song, K. J. Phys. Chem. 1991, 95, 9298. (c) Klippenstein, S. J.; Faulk, J. D.; Dunbar, R. C. J. Chem. Phys. 1993, 98, 243. (d) Osterheld, T. H.; Baer, T.; Brauman, J. I. J. Am. Chem. Soc. 1993 115, 6284. (e) Yim, Y. H.; Kim, M. S. J. Phys. Chem. 1994, 98, 5201.
23. See, for example: (a) Kühlewind, H.; Kiermeier, A.; Neusser, H. J. J. Chem. Phys. 1986, 85, 4427. (b) Lifshitz, C.; Louage, F.; Aviyente, V.; Song, K. J. Phys. Chem. 1991, 95, 9298. (c) Klippenstein, S. J.; Faulk, J. D.; Dunbar, R. C. J. Chem. Phys. 1993, 98, 243. (d) Osterheld, T. H.; Baer, T.; Brauman, J. I. J. Am. Chem. Soc. 1993 115, 6284. (e) Yim, Y. H.; Kim, M. S. J. Phys. Chem. 1994, 98, 5201.
24. See, for example: (a) Shavitt, I. Tetrahedron 1985, 41, 1531. (b) Bauschlicher, C. W., Jr.; Taylor, P. R. J. Chem. Phys. 1986, 85, 6510. (c) Lee, T. J.; Remington, R. B.; Yamaguchi, Y.; Schaefer, H. F. J. Chem. Phys. 1988, 89, 408. (d) Balková, A.; Bartlett, R. J. J. Chem. Phys. 1995, 102, 7116.
25. See, for example: (a) Shavitt, I. Tetrahedron 1985, 41, 1531. (b) Bauschlicher, C. W., Jr.; Taylor, P. R. J. Chem. Phys. 1986, 85, 6510. (c) Lee, T. J.; Remington, R. B.; Yamaguchi, Y.; Schaefer, H. F. J. Chem. Phys. 1988, 89, 408. (d) Balková, A.; Bartlett, R. J. J. Chem. Phys. 1995, 102, 7116.
26. See, for example: (a) Shavitt, I. Tetrahedron 1985, 41, 1531. (b) Bauschlicher, C. W., Jr.; Taylor, P. R. J. Chem. Phys. 1986, 85, 6510. (c) Lee, T. J.; Remington, R. B.; Yamaguchi, Y.; Schaefer, H. F. J. Chem. Phys. 1988, 89, 408. (d) Balková, A.; Bartlett, R. J. J. Chem. Phys. 1995, 102, 7116.
27. See, for example: (a) Shavitt, I. Tetrahedron 1985, 41, 1531. (b) Bauschlicher, C. W., Jr.; Taylor, P. R. J. Chem. Phys. 1986, 85, 6510. (c) Lee, T. J.; Remington, R. B.; Yamaguchi, Y.; Schaefer, H. F. J. Chem. Phys. 1988, 89, 408. (d) Balková, A.; Bartlett, R. J. J. Chem. Phys. 1995, 102, 7116.
28. Davico, G. E.; Bierbaum, V. M.; DePuy, C. H.; Ellison. G. B.; Squires, R. R. J. Am. Chem. Soc. 1995, 117, 2590.
29. Radziszewski, J. G.; Nimlos, M. R.; Winter, P. R.; Ellison, G. B. J. Am. Chem. Soc. 1996, 118, 7400.
30. Meot-Ner (Mautner), M.; Sieck, L. W. J. Phys. Chem. 1986, 90, 6687. See also discussion in: Berkowitz, J.; Ellison, G. B.; Gutman, D. J. Phys. Chem. 1994, 98, 2744 (footnote 205).
31. Meot-Ner (Mautner), M.; Sieck, L. W. J. Phys. Chem. 1986, 90, 6687. See also discussion in: Berkowitz, J.; Ellison, G. B.; Gutman, D. J. Phys. Chem. 1994, 98, 2744 (footnote 205).
32. Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986.
33. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; DeFrees, D. J.; Baker, J.; Stewart, J. J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. GAUSSIAN 94, Gaussian Inc.: Pittsburgh, PA, 1995.
34. Schmidt, M. W.; Baldridge, K. K.; Boatz, J. J.; Elbert, S. T.; Gordon, M. S.; Jensen, J. H.; Koseki, S.; Matsunaga, N.; Nguyen, K. A.; Su, S. J.; Windus, T. L.; Dupuis, M.; Montgomery, J. A. J. Comput. Chem. 1993, 14, 1347.
35. MOLPRO is written by Werner, H. J. and Knowles, P. J. with contributions by Almlof, J., Amos, R. D., Deegan, M., Elbert, S. T., Hampel, K., Meyer, W., Peterson, K., Pitzer, R. M., and Stone, A. J.
36. (a) ACES II, Version 0.2, Stanton, J. F.; Gauss, J.; Watts, J. D.; Lauderdale, W. J.; Bartlett, R. J.; Quantum Theory Project, University of Florida, 1992.
37. (b) Stanton, J. F.; Gauss, J.; Watts, J. D.; Lauderdale, W. J.; Bartlett, R. J. Int. J. Quantum Chem. Symp. 1992, 26, 879.
38. Helgaker, T.; Jensen, J. Aa.; Joergensen, P.; Koch, H.; Olsen, J.; Aagren, H.; Andersen, T.; Bak, K. L.; Bakken, V.; Christiansen, O.; Coriani, S.; Dahle, P.; Dalskov, E. K.; Enevoldsen, T.; Halkier, A.; Heiberg, H.; Jonsson, D.; Kirpekar, S.; Kobayashi, R.; de Meras, A. S.; Mikkelsen, K. V.; Norman, P.; Packer, M. J.; Ruud, K.; Saue, T.; Taylor, P. R.; Vahtras, O. "DALTON 0.10, An Electronic Structure Program", 1996.
39. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
40. (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
41. (c) Miehlich, B.; Savin, A.; Stoll, H.; Preuss, H. Chem. Phys. Lett. 1989, 157, 200.
42. 22 See also: McDouall, J. J.; Peasley, K.; Robb, M. A. Chem. Phys. Lett. 1981, 83, 362.
43. 22 See also: McDouall, J. J.; Peasley, K.; Robb, M. A. Chem. Phys. Lett. 1981, 83, 362.
44. For a recent review of the CAS-MP2 method, see: Andersson, K.; Roos, B. O. In Modern Electronic Structure Theory; Yarkony, D. R., Ed.; World Scientific: Singapore, 1995. For the importance of dynamic electron correlation, see also: Borden, W. T.; Davidson, E. R. Acc. Chem. Res. 1996, 29, 67.
45. For a recent review of the CAS-MP2 method, see: Andersson, K.; Roos, B. O. In Modern Electronic Structure Theory; Yarkony, D. R., Ed.; World Scientific: Singapore, 1995. For the importance of dynamic electron correlation, see also: Borden, W. T.; Davidson, E. R. Acc. Chem. Res. 1996, 29, 67.
46. Bauschlicher, C. W., Jr.; Partridge, H. J. Chem. Phys. 1995, 103, 1788. For an updated HLC factor, see: Bauschlicher, C. W., Jr.; Partridge, H. J. Chem. Phys. 1996, 105, 4398.
47. Bauschlicher, C. W., Jr.; Partridge, H. J. Chem. Phys. 1995, 103, 1788. For an updated HLC factor, see: Bauschlicher, C. W., Jr.; Partridge, H. J. Chem. Phys. 1996, 105, 4398.
48. Stanton, J. F. J. Chem. Phys. 1994, 101, 371.
49. Nicolaides, A.; Borden, W. T. J. Am. Chem. Soc. 1993, 115, 11951 (footnote 35).
50. For an alternative means of correcting errors due to spin-contamination, see: Ochterski, J. W.; Petersson, G. A.; Montgomery, J. A., Jr. J. Chem. Phys. 1996, 104, 2598.
51. See also: Klippenstein, J. S. Submited for publication.
52. -1) higher at the former geometry.
53. (a) Nicolaides, A.; Radom, L. J. Phys. Chem. 1994, 98, 3092.
54. (b) Nicolaides, A.; Radom, L. Mol. Phys. 1996 88, 759.
55. For reviews on G2 and related methods, see: (a) Curtiss, L. A.; Raghavachari, K. In Quantum Mechanical Electronic Structure Calculations with Chemical Accuracy; Langhoff, S. R., Ed.; Kluwer Academic Publishers: Dordrecht, 1995. (b) Raghavachari, K.; Curtiss, L. A. In Modern Electronic Structure Theory; Yarkony, D. R., Ed.; World Scientific: Singapore, 1995.
56. For reviews on G2 and related methods, see: (a) Curtiss, L. A.; Raghavachari, K. In Quantum Mechanical Electronic Structure Calculations with Chemical Accuracy; Langhoff, S. R., Ed.; Kluwer Academic Publishers: Dordrecht, 1995. (b) Raghavachari, K.; Curtiss, L. A. In Modern Electronic Structure Theory; Yarkony, D. R., Ed.; World Scientific: Singapore, 1995.
57. Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. J. Phys. Chem. Ref. Data 1988, 17, Suppl 1.
58. Ervin, K. M.; Gronert, S.; Barlow, S. E.; Gilles, M. K.; Harrison, A. G.; Bierbaum, V. M.; DePuy, C. H.; Lineberger, W. C.; Ellison, G. B. J. Am. Chem. Soc. 1990, 112, 5750.
59. (a) Pekeris, C. L. Phys. Rev. 1962, 126, 1470.
60. (b) Smith, B. J.; Pople, J. A.; Curtiss, L. A.; Radom, L. Aust. J. Chem. Phys. 1992, 45, 285.
61. Hrovat, D.; Borden, W. T. Unpublished results (see note 44 of ref 18).
62. Gunion, R. F.; Gilles, M. K.; Polak, M. L.; Lineberger, W. C. Int. J. Mass Spectrom. Ion Proc. 1992, 117, 601.
63. McKellar, A. R. W.; Bunker, P. R.; Sears, T. J.; Evenson, K. M.; Saykally, R. J.; Langhoff, S. R. J. Chem. Phys. 1983, 79, 5251.
64. 1. We have found this same (incorrect) ordering of states at the CISD/6-31G(d) level of theory even when the Davidson correction for quadruple excitations was included. This is somewhat surprising given that the MP2 level of theory correctly predicts the opposite order of states. This is a manifestation of the sensitivity to the level of theory of the calculated vertical T-S gap.
65. 1 was found to be a second-order saddle point.
66. -1, respectively, at the CAS-MP2/6-311G-(d,p) level).
67. 1 is expected to be very small.
68. CASSCF calculations indicate that this intersystem crossing does not give rise to a reverse dissociation barrier, so that dissociation of a hydrogen atom from the benzene cation proceeds monotonically uphill.
69. Hrusák, J.; Schröder, D.; Iwata, S. J. Chem. Phys. 1997, 106, 7541.
70. -1, in close agreement with their cc-pVDZ value.