Spin-forbidden dehydrogenation of methoxy cation: A statistical view

Physical Chemistry Chemical Physics

Volumn 1, Issue 24, 1999, Pages 5555-5563

  Harvey, Jeremy N ^a   Aschi, Massimiliano ^b  

^a UNIVERSITY OF BRISTOL   (United Kingdom)

^b SAPIENZA UNIVERSITY OF ROME   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

CATION; DEUTERIUM; ISOTOPE;

ARTICLE; CHEMICAL REACTION; ENERGY; GEOMETRY; HYDROGENATION; KINETICS; STATISTICAL ANALYSIS; THEORY;

EID: 0033572562     PISSN: 14639076     EISSN: None     Source Type: Journal    
DOI: 10.1039/a907723e     Document Type: Article

References (88)

1. 1 M. Aschi, J. N. Harvey, C. A. Schalley, D. Schröder and H. Schwarz, Chem. Commun., 1998, 531.
2. 2 As mentioned below, there is in fact an analytical PES available for the singlet system (see ref. 32). However, from the way this surface was constructed, it is unlikely to be truly global, in that it probably does not describe the regions close to the triplet methoxy minimum very accurately.
3. 3 (a) J. C. Lorquet and B. Leyh-Nihant, J. Phys. Chem., 1988, 92, 4778;
4. (b) F. Remacle, D. Dehareng and J. C. Lorquet, J. Phys. Chem., 1988, 92, 4784.
5. 4 For one example among many, see Y. Zeiri, G. Katz, R. Kosloff, M. S. Topaler and D. G. Truhlar, Chem. Phys. Lett., 1999, 300, 523.
6. 5 M. Ben-Nun and T. J. Martinez, J. Chem. Phys., 1998, 108, 7244; X. Sun, H. Wang and W. H. Miller, J. Chem. Phys., 1998, 109, 7064; C. D. Schwieters and G. A. Voth, J. Chem. Phys., 1999, 111, 2869.
7. 5 M. Ben-Nun and T. J. Martinez, J. Chem. Phys., 1998, 108, 7244; X. Sun, H. Wang and W. H. Miller, J. Chem. Phys., 1998, 109, 7064; C. D. Schwieters and G. A. Voth, J. Chem. Phys., 1999, 111, 2869.
8. 5 M. Ben-Nun and T. J. Martinez, J. Chem. Phys., 1998, 108, 7244; X. Sun, H. Wang and W. H. Miller, J. Chem. Phys., 1998, 109, 7064; C. D. Schwieters and G. A. Voth, J. Chem. Phys., 1999, 111, 2869.
9. 6 J. C. Tully, J. Chem. Phys., 1990, 93, 1061, and references cited therein. See also M. S. Topaler, M. D. Hack, T. C. Allison, Y.-P. Liu, S. L. Mielke, D. W. Schwenke and D. G. Truhlar, J. Chem. Phys., 1997, 106, 8699; Y. L. Volobuev, M. D. Hack and D. G. Truhlar, J. Phys. Chem. A, 1999, 103, 6225.
10. 6 J. C. Tully, J. Chem. Phys., 1990, 93, 1061, and references cited therein. See also M. S. Topaler, M. D. Hack, T. C. Allison, Y.-P. Liu, S. L. Mielke, D. W. Schwenke and D. G. Truhlar, J. Chem. Phys., 1997, 106, 8699; Y. L. Volobuev, M. D. Hack and D. G. Truhlar, J. Phys. Chem. A, 1999, 103, 6225.
11. 6 J. C. Tully, J. Chem. Phys., 1990, 93, 1061, and references cited therein. See also M. S. Topaler, M. D. Hack, T. C. Allison, Y.-P. Liu, S. L. Mielke, D. W. Schwenke and D. G. Truhlar, J. Chem. Phys., 1997, 106, 8699; Y. L. Volobuev, M. D. Hack and D. G. Truhlar, J. Phys. Chem. A, 1999, 103, 6225.
12. 7 For reviews on statistical rate theories, see, e.g., (a) W. Forst, Theory of Unimolecular Reactions, Academic Press, New York, 1973;
13. (b) D. G. Truhlar, W. L. Hase and J. T. Hynes, J. Phys. Chem., 1983, 87, 2664;
14. (c) R. G. Gilbert and S. C. Smith, Theory of Unimolecular and Recombination Reactions, Blackwell Scientific Publications, Oxford, UK, 1990;
15. (d) T. Baer and W. L. Hase, Unimolecular Reaction Dynamics, Oxford University Press, Oxford, UK, 1996;
16. (e) D. G. Truhlar, B. C. Garrett and S. J. Klippenstein, J. Phys. Chem., 1996, 100, 12771;
17. (f) W. L. Hase, Acc. Chem. Res., 1998, 31, 659.
18. 8 (a) J. B. Delos, J. Chem. Phys., 1973, 59, 2365;
19. (b) J. C. Tully, J. Chem. Phys., 1974, 61, 61;
20. (c) G. E. Zahr, R. K. Preston and W. H. Miller, J. Chem. Phys., 1975, 62, 1127;
21. (d) E. J. Heller and R. C. Brown, J. Chem. Phys., 1983, 79, 3336;
22. (e) A. J. Marks and D. L. Thompson, J. Chem. Phys., 1992, 96, 1911;
23. (f) S. Hammes-Schiffer and J. C. Tully, J. Chem. Phys., 1995, 103, 8528;
24. (g) M. S. Topaler and D. G. Truhlar, J. Chem. Phys., 1997, 107, 392;
25. (h) D. K. Sahm and D. L. Thompson, Chem. Phys. Lett., 1993, 210, 175.
26. 9 (a) Q. Cui, K. Morokuma and J. M. Bowman, J. Chem. Phys., 1999, 110, 9469;
27. (b) K. Morokuma, Q. Cui and Z. Liu, Faraday Discuss., 1998, 110, 71;
28. (c) Q. Cui and K. Morokuma, Theor. Chem. Acc., 1999, 102, 127.
29. 10 The work described in ref. 9 also uses ab initio calculations to determine the parameters needed for applying a non-adiabatic statistical rate theory. Our approach, developed before publication of these papers, is very similar except for the point discussed below in ref. 21.
30. 11 (a) N. Koga and K. Morokuma, Chem. Phys. Lett., 1985, 119, 371;
31. (b) A. Farazdel and M. Dupuis, J. Comput. Chem., 1991, 12, 276;
32. (c) F. Jensen, J. Am. Chem. Soc., 1992, 114, 1596;
33. (d) D. R. Yarkony, J. Phys. Chem., 1993, 97, 4407;
34. (e) M. J. Bearpark, M. A. Robb and H. B. Schlegel, Chem. Phys. Lett., 1994, 223, 269;
35. (f) K. M. Dunn and K. Morokuma, J. Phys. Chem., 1996, 100, 123;
36. (g) J. M. Anglada and J. M. Bofill, J. Comput. Chem., 1997, 18, 992.
37. 12 J. N. Harvey, M. Aschi, H. Schwarz and W. Koch, Theor. Chem. Acc., 1998, 99, 95.
38. 13 W. H. Press, S. A. Teukolsky, W. T. Vetterling and B. P. Flannery, Numerical Recipes in Fortran 77, Cambridge University Press, Cambridge, UK, 1996.
39. 14 See, for example, (a) D. R. Yarkony, J. Am. Chem. Soc., 1992, 114, 5406;
40. (b) J. E. Stevens, Q. Cui and K. Morokuma, J. Chem. Phys., 1998, 108, 1544;
41. (c) A. A. Korkin, M. Nooijen, R. J. Bartlett and K. O. Christe, J. Phys. Chem. A, 1998, 102, 1837;
42. (d) D. R. Yarkony, J. Phys. Chem. A, 1998, 102, 5305;
43. (e) S. Wilsey, F. Bernardi, M. Olivucci, M. A. Robb, S. Murphy and W. Adam, J. Phys. Chem. A, 1999, 103, 1669;
44. (f) A. L. Kaledin, Q. Cui, M. C. Heaven and K. Morokuma, J. Chem. Phys., 1999, 111, 5004;
45. (g) M. R. Manaa and C. F. Chabalowski, Chem. Phys. Lett., 1999, 300, 619.
46. 15 (a) J. N. Harvey, D. Schröder and H. Schwarz, Bull. Soc. Chim. Belg., 1997, 106, 447;
47. (b) C. A. Schalley, J. N. Harvey, D. Schröder and H. Schwarz, J. Phys. Chem. A, 1998, 102, 1021;
48. (c) C. A. Schalley, S. Blanksby, J. N. Harvey, D. Schröder, W. Zummack, J. H. Bowie and H. Schwarz, Eur. J. Org. Chem., 1998, 1, 987;
49. (d) M. Aschi, F. Grandinetti and V. Vinciguerra, Chem. Eur. J., 1988, 4, 2366;
50. (e) D. Schröder, C. Heinemann, H. Schwarz, J. N. Harvey, S. Dua, S. J. Blanksby and J. H. Bowie, Chem. Eur. J., 1998, 4, 2550;
51. (f) C. Rue, P. B. Armentrout, I. Kretzschmar, D. Schröder, J. N. Harvey and H. Schwarz, J. Chem. Phys., 1999, 110, 7858;
52. (g) M. Aschi and J. N. Harvey, J. Chem. Soc., Perkin Trans. 2, 1999, 1059;
53. (h) M. Aschi and F. Grandinetti, J. Chem. Phys., 1999, 111, 6759;
54. (i) K. M. Smith, J. N. Harvey and R. Poli, Organometallics, submitted.
55. 16 For studies of reaction mechanisms involving conical intersections, see e.g. M. Garavelli, B. Frabboni, M. Fato, P. Celani, F. Bernardi, M. A. Robb and M. Olivucci, J. Am. Chem. Soc., 1999, 121, 1537; D. R. Yarkony, Acc. Chem. Res., 1998, 31, 511; F. Bernardi, M. Olivucci and M. A. Robb, Chem. Soc. Rev., 1996, 321.
56. 16 For studies of reaction mechanisms involving conical intersections, see e.g. M. Garavelli, B. Frabboni, M. Fato, P. Celani, F. Bernardi, M. A. Robb and M. Olivucci, J. Am. Chem. Soc., 1999, 121, 1537; D. R. Yarkony, Acc. Chem. Res., 1998, 31, 511; F. Bernardi, M. Olivucci and M. A. Robb, Chem. Soc. Rev., 1996, 321.
57. 16 For studies of reaction mechanisms involving conical intersections, see e.g. M. Garavelli, B. Frabboni, M. Fato, P. Celani, F. Bernardi, M. A. Robb and M. Olivucci, J. Am. Chem. Soc., 1999, 121, 1537; D. R. Yarkony, Acc. Chem. Res., 1998, 31, 511; F. Bernardi, M. Olivucci and M. A. Robb, Chem. Soc. Rev., 1996, 321.
58. 17 K. Ohta and K. Morokuma, J. Phys. Chem., 1987, 91, 401; A. Farazdel, M. Dupuis, E. Clementi and A. Avitam, J. Am. Chem. Soc., 1990, 112, 4206;
59. 17 K. Ohta and K. Morokuma, J. Phys. Chem., 1987, 91, 401; A. Farazdel, M. Dupuis, E. Clementi and A. Avitam, J. Am. Chem. Soc., 1990, 112, 4206;
60. O. Kitao, H. Ushiyama and N. Miura, J. Chem. Phys., 1999,110, 2936.
61. 18 W. H. Miller, N. C. Handy and J. E. Adams, J. Chem. Phys., 1980, 72, 99.
62. 2 MECP studied in ref. 9, where only real frequencies are obtained. This is only by chance, however.
63. 20 See, e.g. refs. 8a-c,e,h; (a) A. J. Lorquet, J. C. Lorquet and W. Forst, Chem. Phys., 1980, 51, 253;
64. (b) A. H. H. Chang and D. R. Yarkony, J. Chem. Phys., 1993, 99, 6824.
65. 21 N. Nakamura and S. Kato, J. Chem. Phys., 1999, 110, 9937.
66. 22 For leading references, see (a) M. M. Bursey, J. R. Hass, D. J. Harvan and C. A. Parker, J. Am. Chem. Soc., 1979, 101, 5485;
67. (b) P. C. Burgers and J. L. Holmes, Org. Mass Spectrom., 1984, 19, 452;
68. (c) S.-C. Kuo, Z. Zhang, R. B. Klemm, J. F. Liebman, L. J. Stief and F. L. Nesbitt, J. Phys. Chem., 1994, 98, 4026.
69. + system, see ref. 14a, L. A. Curtiss, L. D. Kock and J. A. Pople, J. Chem. Phys., 1991, 95, 4040.
70. 24 T. H. Dunning, Jr., J. Chem. Phys., 1989, 90, 1007.
71. 25 The values reported in ref. 1 are in each case the magnitude of the two identical non-zero singlet-triplet matrix elements, which explains the apparent difference with the rms values mentioned here.
72. 26 L. A. Curtiss, K. Raghavachari, P. C. Redfern, V. Rassolov and J. A. Pople, J. Chem. Phys., 1998, 109, 7764.
73. 27 For an example of an RRKM calculation using anharmonic vibrational energy levels, see K. M. Christoffel and J. M. Bowman, J. Phys. Chem. A, 1999, 103, 3020.
74. 28 J. Villá, J. C. Corchado, A. González-Lafont, J. M. Lluch and D. G. Truhlar, J. Phys. Chem. A, 1999, 103, 5061, and references therein.
75. 29 J. J. Wang, D. J. Smith and R. Grice, J. Phys. Chem. A, 1997, 101, 3293 and references therein.
76. 30 B. Leyh-Nihant and J. C. Lorquet, J. Chem. Phys., 1988, 88, 5606.
77. 31 For a discussion of such cases, see L. Salem and C. Rowland, Angew. Chem., Int. Ed. Engl., 1972, 11, 92.
78. 32 T. G. Lee, S. C. Park and M. S. Kim, J. Chem. Phys., 1996, 104, 4517, see also Y. M. Rhee, T. G. Lee, S. C. Park and M. S. Kim, J. Chem. Phys., 1997, 106, 1003.
79. 32 T. G. Lee, S. C. Park and M. S. Kim, J. Chem. Phys., 1996, 104, 4517, see also Y. M. Rhee, T. G. Lee, S. C. Park and M. S. Kim, J. Chem. Phys., 1997, 106, 1003.
80. 33 Gamess-USA (version of 1st December 1998), M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. J. Su and T. L. Windus together with M. Dupuis and J. A. Montgomery, J. Comput. Chem., 1993, 14, 1347.
81. 34 M. P. Allen and D. J. Tildesley, Computer Simulation of Liquids, Clarendon Press, Oxford, UK, 1989.
82. 35 R. Schinke, Photodissociation Dynamics, Cambridge University Press, Cambridge, UK, 1993, ch. 5, and references therein. Also see R. Schinke, J. Phys. Chem., 1988, 92, 3195.
83. 35 R. Schinke, Photodissociation Dynamics, Cambridge University Press, Cambridge, UK, 1993, ch. 5, and references therein. Also see R. Schinke, J. Phys. Chem., 1988, 92, 3195.
84. + minimum. The KER results are derived from the remaining 341 (333) trajectories.
85. 37 E. Uggerud and T. Helgaker, J. Am. Chem. Soc., 1992, 114, 4265.
86. 38 G. Hvistendahl and E. Uggerud, Org. Mass. Spectrom., 1991, 26, 67.
87. 39 For a review on choosing initial conditions for classical trajectories, see G. H. Peslherbe, H. Wang and W. L. Hase, Adv. Chem. Phys., 1999, 105, 171.
88. 40 W. Chen, W. L. Hase and H. B. Schlegel, Chem. Phys. Lett., 1994, 228, 436.