Pauling's electronegativity equation and a new corollary accurately predict bond dissociation enthalpies and enhance current understanding of the nature of the chemical bond

Journal of Organic Chemistry

Volumn 68, Issue 8, 2003, Pages 3158-3172

  Matsunaga, Nikita ^a   Rogers, Donald W ^a   Zavitsas, Andreas A ^a  

^a LONG ISLAND UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ELECTRONEGATIVITY;

DISSOCIATION; ELECTRONIC STRUCTURE; ENTHALPY; HYDROGEN; MOLECULAR STRUCTURE; STEREOCHEMISTRY; SUBSTITUTION REACTIONS;

CHEMICAL BONDS;

AROMATIC COMPOUND;

ACCURACY; ARTICLE; AUTOOXIDATION; CHEMICAL REACTION; CHEMICAL STRUCTURE; COVALENT BOND; DISSOCIATION; ENTHALPY; MATHEMATICAL MODEL; MOLECULAR STABILITY; STEREOSPECIFICITY;

EID: 0037453558     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo020650g     Document Type: Article

References (123)

1. Pauling, L. J. Am. Chem. Soc. 1932, 54, 3570-3582. Pauling, L. The Nature of the Chemical Bond and the Structure of Molecules and Crystals, 3rd ed.; Cornell University Press: Ithaca, NY, 1960. Pauling also considered a "geometric mean" alternative equation, because of the alkali metal hydrides, but concluded that "We shall accordingly use the arithmetic mean...", i.e., eq 1; his widely quoted electronegativity values are based on eq 1.
2. Pauling, L. J. Am. Chem. Soc. 1932, 54, 3570-3582. Pauling, L. The Nature of the Chemical Bond and the Structure of Molecules and Crystals, 3rd ed.; Cornell University Press: Ithaca, NY, 1960. Pauling also considered a "geometric mean" alternative equation, because of the alkali metal hydrides, but concluded that "We shall accordingly use the arithmetic mean...", i.e., eq 1; his widely quoted electronegativity values are based on eq 1.
3. Ochterski, J. W.; Petersson, G. A.; Wiberg, K. B. J. Am. Chem. Soc. 1995, 117, 11299-11308.
4. (a) Sanderson, R. T. Polar Covalence; Academic Press: New York, 1983.
5. (b) Yuan, H. Acta Chim. Sin. 1964, 30, 341.
6. (c) Luo, Y.-R.; Benson, S. W. Acc. Chem. Res. 1992, 25, 375-381 and references therein.
7. (d) Suresh, C. H.; Koga, N. J. Am. Chem. Soc. 2002, 124, 1790-1797.
8. (a) Murphy, L. R.; Meek, T. L.; Allred, A. L.; Allen, L. C. J. Phys. Chem. A 2000, 104, 5867-5871.
9. (b) Perks, H. M.; Liebman, J. F. Struct. Chem. 2000, 11, 375-378 and references therein.
10. Some recent examples of this widespread practice include: Fossey, J.; Lefort, D.; Sorba, J. Free Radicals in Inorganic Chemistry; Wiley: Chichester, UK, 1995; p 33. Mayer, P. M.; Glukhovtsev, M. N.; Gauld, J. W.; Radom, L. J. Am. Chem. Soc. 1997, 119, 12889-12895. Wayner, D. D.; Clark, K. B.; Rauk, A.; Yu, D.; Armstrong, D. A. J. Am. Chem. Soc. 1997, 119, 8925-8932. Carey, F. A. Organic Chemistry, 5th ed.; McGraw-Hill: Boston, 2002; p 171. Solomons, T. W. G.; Fryhle, G. B. Organic Chemistry, 7th ed.; John Wiley & Sons: New York, 2000; p 436.
11. Some recent examples of this widespread practice include: Fossey, J.; Lefort, D.; Sorba, J. Free Radicals in Inorganic Chemistry; Wiley: Chichester, UK, 1995; p 33. Mayer, P. M.; Glukhovtsev, M. N.; Gauld, J. W.; Radom, L. J. Am. Chem. Soc. 1997, 119, 12889-12895. Wayner, D. D.; Clark, K. B.; Rauk, A.; Yu, D.; Armstrong, D. A. J. Am. Chem. Soc. 1997, 119, 8925-8932. Carey, F. A. Organic Chemistry, 5th ed.; McGraw-Hill: Boston, 2002; p 171. Solomons, T. W. G.; Fryhle, G. B. Organic Chemistry, 7th ed.; John Wiley & Sons: New York, 2000; p 436.
12. Some recent examples of this widespread practice include: Fossey, J.; Lefort, D.; Sorba, J. Free Radicals in Inorganic Chemistry; Wiley: Chichester, UK, 1995; p 33. Mayer, P. M.; Glukhovtsev, M. N.; Gauld, J. W.; Radom, L. J. Am. Chem. Soc. 1997, 119, 12889-12895. Wayner, D. D.; Clark, K. B.; Rauk, A.; Yu, D.; Armstrong, D. A. J. Am. Chem. Soc. 1997, 119, 8925-8932. Carey, F. A. Organic Chemistry, 5th ed.; McGraw-Hill: Boston, 2002; p 171. Solomons, T. W. G.; Fryhle, G. B. Organic Chemistry, 7th ed.; John Wiley & Sons: New York, 2000; p 436.
13. Some recent examples of this widespread practice include: Fossey, J.; Lefort, D.; Sorba, J. Free Radicals in Inorganic Chemistry; Wiley: Chichester, UK, 1995; p 33. Mayer, P. M.; Glukhovtsev, M. N.; Gauld, J. W.; Radom, L. J. Am. Chem. Soc. 1997, 119, 12889-12895. Wayner, D. D.; Clark, K. B.; Rauk, A.; Yu, D.; Armstrong, D. A. J. Am. Chem. Soc. 1997, 119, 8925-8932. Carey, F. A. Organic Chemistry, 5th ed.; McGraw-Hill: Boston, 2002; p 171. Solomons, T. W. G.; Fryhle, G. B. Organic Chemistry, 7th ed.; John Wiley & Sons: New York, 2000; p 436.
14. Some recent examples of this widespread practice include: Fossey, J.; Lefort, D.; Sorba, J. Free Radicals in Inorganic Chemistry; Wiley: Chichester, UK, 1995; p 33. Mayer, P. M.; Glukhovtsev, M. N.; Gauld, J. W.; Radom, L. J. Am. Chem. Soc. 1997, 119, 12889-12895. Wayner, D. D.; Clark, K. B.; Rauk, A.; Yu, D.; Armstrong, D. A. J. Am. Chem. Soc. 1997, 119, 8925-8932. Carey, F. A. Organic Chemistry, 5th ed.; McGraw-Hill: Boston, 2002; p 171. Solomons, T. W. G.; Fryhle, G. B. Organic Chemistry, 7th ed.; John Wiley & Sons: New York, 2000; p 436.
15. Leffler, J. E. An Introduction to Free Radicals; Wiley: New York, 1993.
16. Winiker, R.; Beckhaus, H.-D.; Rüchardt, C. Chem. Ber. 1980, 113, 3456-3476.
17. Afeefy, H. Y.; Liebman, J. F.; Stein, S. E. Neutral Thermochemical Data. In NIST Chemistry WebBook, NIST Standard Reference Database Number 69; Linstrom, P. J., Mallard, W. G., Eds.; July 2001, National Institute of Standards and Technology, Gaithersburg MD, 20899 (http://webbook.nist.gov). IE and AE data compiled by Lias, G. S., Rosenstock, H. M., Draxl, K., Steiner, B. W., Herron, J. T., Holmes, J. L., Levin, R. D., Liebman, J. F., Kafafi, S, A.
18. fH° of the acetyl radical from previous editions, all other values were not.
19. Lias, S. G.; Liebman, J. F.; Levin, R. D.; Kafafi, S. A. NIST Standard Reference Database 25; Stein, S. E., Ed.; 1994. Chemical Kinetics and Thermodynamics Division, National Institute of Standards and Technology, Gaithersburg, MD 20899. Version 2.0.
20. (a) Liebman, J. F.; Martinho Simões, J. A.; Slayden, S. W. Struct. Chem. 1995, 6, 263.
21. (b) Luo, Y.-R.; Benson, S. W. J. Phys. Chem. 1997, 101, 3042-3044.
22. Schaffer, F.; Verevkin, S. P.; Rieger, H,-J.; Beckhaus, H.-D.; Rüchardt, C. Liebigs Ann./Recueil 1997, 1333-1344.
23. (a) Benson, S. W.; Shaw, R. Adv. Chem. Ser. 1968, 75, 287.
24. (b) Rüchardt, C. Angew. Chem., Int. Ed. Engl. 1970, 9, 830.
25. (c) Winiker, R.; Beckhaus, H.-D.; Rüchardt. C. Chem. Ber. 1980, 113, 3456-3476. Kratt, G.; Beckhaus, H.-D.; Bernlöhr, W.; Rüchardt, C. Thermochim. Acta 1983, 62,279-294. Rüchardt, C.;Beckhaus, H.-D. Angew. Chem., Int. Ed. Engl. 1985, 24, 529-538. Rüchardt, C.; Beckhaus, H.-D. Top. Curr. Chem. 1986, 130, 1-22. Welle, F. M.; Beckhaus, H.-D.; Rüchardt, C. J. Org. Chem. 1997, 62, 552-558. Brocks, J. J.; Beckhaus, H.-D.; Beckwith, A. L. J.; Rüchardt, C. J. Org. Chem. 1998, 63, 1935-1943 and references therein.
26. (c) Winiker, R.; Beckhaus, H.-D.; Rüchardt. C. Chem. Ber. 1980, 113, 3456-3476. Kratt, G.; Beckhaus, H.-D.; Bernlöhr, W.; Rüchardt, C. Thermochim. Acta 1983, 62,279-294. Rüchardt, C.;Beckhaus, H.-D. Angew. Chem., Int. Ed. Engl. 1985, 24, 529-538. Rüchardt, C.; Beckhaus, H.-D. Top. Curr. Chem. 1986, 130, 1-22. Welle, F. M.; Beckhaus, H.-D.; Rüchardt, C. J. Org. Chem. 1997, 62, 552-558. Brocks, J. J.; Beckhaus, H.-D.; Beckwith, A. L. J.; Rüchardt, C. J. Org. Chem. 1998, 63, 1935-1943 and references therein.
27. (c) Winiker, R.; Beckhaus, H.-D.; Rüchardt. C. Chem. Ber. 1980, 113, 3456-3476. Kratt, G.; Beckhaus, H.-D.; Bernlöhr, W.; Rüchardt, C. Thermochim. Acta 1983, 62,279-294. Rüchardt, C.;Beckhaus, H.-D. Angew. Chem., Int. Ed. Engl. 1985, 24, 529-538. Rüchardt, C.; Beckhaus, H.-D. Top. Curr. Chem. 1986, 130, 1-22. Welle, F. M.; Beckhaus, H.-D.; Rüchardt, C. J. Org. Chem. 1997, 62, 552-558. Brocks, J. J.; Beckhaus, H.-D.; Beckwith, A. L. J.; Rüchardt, C. J. Org. Chem. 1998, 63, 1935-1943 and references therein.
28. (c) Winiker, R.; Beckhaus, H.-D.; Rüchardt. C. Chem. Ber. 1980, 113, 3456-3476. Kratt, G.; Beckhaus, H.-D.; Bernlöhr, W.; Rüchardt, C. Thermochim. Acta 1983, 62,279-294. Rüchardt, C.;Beckhaus, H.-D. Angew. Chem., Int. Ed. Engl. 1985, 24, 529-538. Rüchardt, C.; Beckhaus, H.-D. Top. Curr. Chem. 1986, 130, 1-22. Welle, F. M.; Beckhaus, H.-D.; Rüchardt, C. J. Org. Chem. 1997, 62, 552-558. Brocks, J. J.; Beckhaus, H.-D.; Beckwith, A. L. J.; Rüchardt, C. J. Org. Chem. 1998, 63, 1935-1943 and references therein.
29. (c) Winiker, R.; Beckhaus, H.-D.; Rüchardt. C. Chem. Ber. 1980, 113, 3456-3476. Kratt, G.; Beckhaus, H.-D.; Bernlöhr, W.; Rüchardt, C. Thermochim. Acta 1983, 62,279-294. Rüchardt, C.;Beckhaus, H.-D. Angew. Chem., Int. Ed. Engl. 1985, 24, 529-538. Rüchardt, C.; Beckhaus, H.-D. Top. Curr. Chem. 1986, 130, 1-22. Welle, F. M.; Beckhaus, H.-D.; Rüchardt, C. J. Org. Chem. 1997, 62, 552-558. Brocks, J. J.; Beckhaus, H.-D.; Beckwith, A. L. J.; Rüchardt, C. J. Org. Chem. 1998, 63, 1935-1943 and references therein.
30. (c) Winiker, R.; Beckhaus, H.-D.; Rüchardt. C. Chem. Ber. 1980, 113, 3456-3476. Kratt, G.; Beckhaus, H.-D.; Bernlöhr, W.; Rüchardt, C. Thermochim. Acta 1983, 62,279-294. Rüchardt, C.;Beckhaus, H.-D. Angew. Chem., Int. Ed. Engl. 1985, 24, 529-538. Rüchardt, C.; Beckhaus, H.-D. Top. Curr. Chem. 1986, 130, 1-22. Welle, F. M.; Beckhaus, H.-D.; Rüchardt, C. J. Org. Chem. 1997, 62, 552-558. Brocks, J. J.; Beckhaus, H.-D.; Beckwith, A. L. J.; Rüchardt, C. J. Org. Chem. 1998, 63, 1935-1943 and references therein.
31. Luo, Y.-R.; Holmes, J. L. J. Phys. Chem. 1994, 98, 303-312.
32. Shurki, A.; Hiberty, P. C.; Shaik, S. J. Am. Chem. Soc. 1999, 121, 822-834.
33. f° adopted for the radicals in this work, Table 1.
34. Walling, C. Free Radicals in Solution; Wiley: New York, 1957; pp 51-52.
35. Nicholas, A. M. de P.; Arnold, D. R. Can. J. Chem. 1984, 62, 1850-1859.
36. (a) Bordwell, F. G.; Cheng, J.-P.; Bausch, M. J.; Bares, J. E. J. Phys, Org. Chem. 1988, 1, 209-223.
37. (b) Bordwell, F. G.; Zhang, X.-M.; Satish, A. V.; Cheng, J.-P. J. Am. Chem. Soc. 1994, 116, 6605-6610.
38. (c) Nau, W. M. J. Org. Chem. 1996, 61, 8312-8314.
39. (d) Nau, W. M. J. Phys. Org. Chem. 1997, 10, 445-455.
40. (e) Brink, T.; Heaberlein, M.; Jonsson, M. J. Am. Chem. Soc. 1997, 119, 4239-4244.
41. (f) Pratt, D. A.; Wright, J. S.; Ingold, K. U. J. Am. Chem. Soc. 1999, 121, 4877-4882.
42. (g) Cheng, J.-P.; Liu, B.; Zhao, Y.; Wen, Z.; Sun, Y. J. Am. Chem. Soc. 2000, 122, 9987-9992.
43. (h) Lü, J.-M.; Wittbrodt, J. M.; Wan, K.; Wen, Z.; Schlegel, H. B.; Wang, P. G.; Cheng, J.-P. J. Am. Chem. Soc. 2001, 123, 2903-2904.
44. (i) Pratt, D. A.; de Heer, M. I.; Mulder, P.; Ingold, K. U. J. Am. Chem. Soe. 2001, 123, 5518-5526.
45. Zavitsas, A. A.; Pinto, J. A. P. J. Am. Chem. Soc. 1972, 94, 7390-7396.
46. Becerra, R.; Walsh, R. In The Chemistry of Organic Silicon Compounds; Rappoport, Z. Apeloig, Y., Eds.; Wiley: New York, 1998; Vol. 2, pp 153-180.
47. Almenningen, A.; Bastiansen, O.; Fernholt, L.; Cyvin, B. N.; Cyvin, S. J.; Samdal, S. J. Mol. Struct. 1985, 128, 59-76. Almenningen, A.; Bastiansen, O.; Gundersen, S.; Samdal, S.; Skancke, A. J. Mol. Struct. 1985, 128, 95-114. Pullham, R. J.; Steele, D. J. Raman Spectrosc. 1984, 15, 211. Chandrakumar, T.; Polson, J. M.; Burnell, E. E. J. Magn. Reson. Ser. A 1996, 118, 264-271. Coplanarity was reported in the solid, but crystal energy effects are operative.
48. Almenningen, A.; Bastiansen, O.; Fernholt, L.; Cyvin, B. N.; Cyvin, S. J.; Samdal, S. J. Mol. Struct. 1985, 128, 59-76. Almenningen, A.; Bastiansen, O.; Gundersen, S.; Samdal, S.; Skancke, A. J. Mol. Struct. 1985, 128, 95-114. Pullham, R. J.; Steele, D. J. Raman Spectrosc. 1984, 15, 211. Chandrakumar, T.; Polson, J. M.; Burnell, E. E. J. Magn. Reson. Ser. A 1996, 118, 264-271. Coplanarity was reported in the solid, but crystal energy effects are operative.
49. Almenningen, A.; Bastiansen, O.; Fernholt, L.; Cyvin, B. N.; Cyvin, S. J.; Samdal, S. J. Mol. Struct. 1985, 128, 59-76. Almenningen, A.; Bastiansen, O.; Gundersen, S.; Samdal, S.; Skancke, A. J. Mol. Struct. 1985, 128, 95-114. Pullham, R. J.; Steele, D. J. Raman Spectrosc. 1984, 15, 211. Chandrakumar, T.; Polson, J. M.; Burnell, E. E. J. Magn. Reson. Ser. A 1996, 118, 264-271. Coplanarity was reported in the solid, but crystal energy effects are operative.
50. Almenningen, A.; Bastiansen, O.; Fernholt, L.; Cyvin, B. N.; Cyvin, S. J.; Samdal, S. J. Mol. Struct. 1985, 128, 59-76. Almenningen, A.; Bastiansen, O.; Gundersen, S.; Samdal, S.; Skancke, A. J. Mol. Struct. 1985, 128, 95-114. Pullham, R. J.; Steele, D. J. Raman Spectrosc. 1984, 15, 211. Chandrakumar, T.; Polson, J. M.; Burnell, E. E. J. Magn. Reson. Ser. A 1996, 118, 264-271. Coplanarity was reported in the solid, but crystal energy effects are operative.
51. Abboud, J. M.; Jimenez, P.; Roux, V.; Turrion, C.; Lopez-Mardomingo, C.; Podosennin, A.; Rogers, D. W.; Liebman, J. F. J. Phys. Org. Chem. 1995, 8, 15.
52. Cochran, J. C.; Hagen, K.; Paulen, G.; Shen, Q.; Tom, S. J. Mol. Struct. 1997, 413, 313-326.
53. Facchine, K. L.; Staley, S. W.; Zijl, P. C. M. van; Mishra, P. K.; Bothner-By, A. A. J. Am. Chem. Soc. 1988, 110, 4900-4905.
54. Carriera, L. A.; Towns, T. G. J. Chem. Phys. 1975, 63, 5283.
55. Davis, H. E.; Allinger, N. L.; Rogers, D. W. J. Org. Chem. 1985, 50, 3601.
56. Roth, W. R.; Adamczak, O.; Breuckman, R.; Lennartz, H.-W.; Boese, R. Chem. Ber. 1991, 124, 2499-2521.
57. Rogers, D. W.; Dagdagan, O. A.; Allinger, N. L. J. Am. Chem. Soc. 1979, 101, 671-676.
58. Curtiss, L. A.; Raghavachari, K.; Redfern, P. C.; Rassolov, V.; Pople, J. A. J. Chem. Phys. 1998, 109, 7764-7776.
59. "3d Mol" file, compiled by Irikura, K. K., ref 8, based on PM3 calculations.
60. -1.
61. (b) Neugebauer Crawford, S. M.; Taha, A. N.; True, N. S.; LeMaster, C. B. J. Phys. Chem. A 1997, 101, 4699-4706.
62. (c) Tsuzuki, S.; Tanabe, K. J. Chem. Soc., Perkin Trans. 2 1991, 8, 1255.
63. Taha, A. N.; True, N. S. J. Phys. Chem. A 2000, 104, 8609-8616.
64. Mo, Y.; Lin, Z. J. Chem. Phys. 1996, 105, 1046-1051 and references therein.
65. (a) Wiberg, K. B. J. Org. Chem. 1991, 56, 544-550.
66. (b) Becerra, R.; Walsh, R. J. Phys. Chem. A 1997, 101, 8959-8963.
67. -1, which includes ZPE; 1/2hv of the S-S stretching frequency is 0.76.
68. 8 D[MeS-SMe] = 60.0.
69. (a) Baboul, A. G.; Schlegel, H. B. J. Am. Chem. Soc. 1996, 118, 8444-8451.
70. (b) Boyd, S. R.; Boyd, R. J. J. Am. Chem. Soc. 1997, 119, 4214-4219; quoted at 298 K.
71. Montgomery, J. A. Jr.; Frisch, M. J.; Ochterski, J. W.; Petersson, G. A. J. Chem. Phys. 2000, 112, 6532-6542.
72. Colussi, A. J.; Zabel, F.; Benson, S. W. Int. J. Chem. Kinet. 1977, 9, 161-178. Very low-pressure pyrolysis.
73. Literature values: (a) 30.0 ± 1.1 from group additivity: Benson, S. W. J. Phys. Chem. 1996, 100, 13544-13547.
74. (b) 30.9 ± 0.8: Slagle, I. R.; Gutman, D. J. Am. Chem. Soc. 1985, 107, 5342.
75. 32.2: ref 9.
76. (c) 32.7 ± 0.9: Knyazev, V. D.; Slagle, I. R. J. Phys. Chem. A 1998, 102, 1770-1778.
77. Knyazev, V. D.; Slagle, I. R. J. Phys. Chem. A 1998, 102, 8932-8940.
78. Elmaimouni, L.; Minetti, R.; Sawyersin, J. P.; Devolder, P. Int. J. Chem. Kinet. 1993, 25, 399-414.
79. (a) Maillard, B.; Ingold, K. U.; Scaiano, J. C. J. Am. Chem. Soc. 1983, 105, 5095.
80. (b) Platz, J.; Nielsen, O. J.; Wallington, T. J.; Ball, J. C.; Hurley, M. D.; Straccia, A. M.; Schneider, W. F.; Sehested, J. J. Phys. Chem A 1998, 102, 7964-7974.
81. Mckay, D. J.; Wright, J. S. J. Am. Chem. Soc. 1998, 120, 1003-1013; G2(MP2) at 0 K.
82. Krasnoperov, L. V.; Kalinovski, I. J.; Niiranen, J. T.; Gutman, D. J. Phys. Chem. A 1997, 101, 4929-4938.
83. Bartberger, M. D.; Mannion, J. D.; Powel, S. C.; Stamler, J. S.; Houk, K. N.; Toone, E. J. J. Am. Chem. Soc. 2001, 123, 8868-8869.
84. Zhang, D.; Zhang, R.; Park, J.; North, S. W. J. Am. Chem. Soc. 2002, 124, 9600-9605; B3LYP/6-31G(d,p) and CCSD/6-31G
85. Vollhardt, K. P.; Schore, N. E. Organic Chemistry, Structure and Function, 4th ed.; W. H. Freeman and Co.: New York, 2002; p 436.
86. Ponec, R.; Roithová, J.; Gironés, X.; Lain, L.; Torre, A.; Bochicchio, R. J. Phys. Chem. A 2002, 106, 1019-1025 and references therein.
87. Epiotis, N. E. Top. Curr. Chem. 1989, 130, 47-166 and particularly p 126.
88. Zavitsas, A. A. J. Am. Chem. Soc. 1991, 113, 4755-4767 and references therein. Values converted to 298 K.
89. Wang, Y.-C.; Kajitani, M.; Kasahara, S.; Baba, M.; Ishikawa, K.; Kat6, H. J. Chem. Phys. 1991, 95, 6229-6237. Value converted to 298 K.
90. Amiot, C.; Vergès, J. J. Chem. Phys. 2000, 112, 7068-7074. Value converted to 298 K.
91. (a) Chase, M. W., Jr.; Davies, C. A.; Downey, J. R., Jr.; Frurip, D. J.; McDonald, R. A.; Syverud, A. N. J. Phys. Chem. Ref. Data 1985, 14, Supplement no. 1 (JANAF Thermochemical Tables).
92. (b) Clyne, M. A. A.; McDermid, I. S. J. Chem. Soc., Faraday Trans. 2 1978, 74, 644 and 1644.
93. (c) Visscher, L.; Dyall, K. G. J. Chem. Phys. 1996, 104, 9040-9046; CCSD level.
94. Griffiths, J. A.; Jung, K.-W.; El-Sayed, M. A. J. Phys. Chem. 1996, 100, 7989-7996.
95. Allen, L. C. J. Am. Chem. Soc. 1989, 111, 9003-9014. Luo, Y.-R.; Benson, S. W. J. Phys. Chem. 1989, 93, 7333-7335.
96. Allen, L. C. J. Am. Chem. Soc. 1989, 111, 9003-9014. Luo, Y.-R.; Benson, S. W. J. Phys. Chem. 1989, 93, 7333-7335.
97. Luo, H.-R.; Pacey, P. D. J. Am. Chem. Soc. 1991, 113, 1465-1466.
98. Boyd, R. J.; Boyd, S. L. J. Am. Chem. Soc. 1992, 114, 1652-1655.
99. McMillen, D. F.; Golden, D. M. Annu. Rev. Phys. Chem. 1982, 33, 493-532.
100. Reddy, R. R.; Rao, T. V. R.; Viswanath, R. J. Am. Chem. Soc. 1988, 111, 2914.
101. Bratsch, S. G. J. Chem. Educ. 1984, 61, 588.
102. Also independently proposed by Smith, D. W. J. Phys. Chem. A 2002, 106, 5951-5952.
103. Chen, E. C. M.; Welk, N.; Chen, E.; Wentworth, W. E. J. Phys. Chem. A 1999, 103, 9072-9079.
104. Zavitsas, A. A. J. Phys. Chem. 1987, 91, 5573-5577.
105. Melius, C. F.; Ho, P. J. Phys. Chem. 1991, 95, 1410-1419.
106. Bickelhaupt, F. M.; Ziegler, T.; Schleyer, P. v. R. Organometallics 1996, 15, 1477-1487.
107. Ho, P.; Colvin, M. E.; Melius, C. F. J. Phys. Chem. A 1997, 101, 9470-9488.
108. Ventura, O. N.; Kieninger, M.; Cachau, R. E. J. Phys. Chem. A 1999, 103, 147-151.
109. fÉ[PhOOH] = -6.1 and enthalpies of formation of PhO· and HO· adopted for this work.
110. Jung, D.; Chen, C.-J.; Bozzelli, J. W. J. Phys. Chem. A 2000, 104, 9581-9590.
111. Ruscic, B.; Appelman, E. H.; Berkowitz, J. J. Chem. Phys. 1991, 95, 7957-7961.
112. 2] would be insignificant.
113. 2] would be insignificant.
114. 2] would be insignificant.
115. Rablen, P. R.; Hartwig, J. F. J. Am. Chem. Soc. 1996, 118, 4648-4653.
116. 8
117. Benson, S. W.; Garland, L. J. J. Phys. Chem. 1991, 95, 4915-4918.
118. (a) Haworth, N. L.; Smith, M. H.; Bacskay, G. B.; Mackie, J. C. J. Phys. Chem. A 2000, 104, 7600-7611.
119. (b) Parthiban, S.; Martin, J. M. L.; Liebman, J. F. Mol. Phys. 2002, 100, 453-464.
120. (c) Manion, J. A. J. Phys. Chem. Ref. Data 2002, 31, 123-172.
121. Cohen, N.; Benson, S. W. Chem. Rev. 1993, 93, 2419.
122. Lay, T. H.; Bozzelli, J. W. J. Phys. Chem. 1997, 101, 9505-9510.
123. Zhu, R.; Lin, M. C. PhysChemComm 2001, 23, 1-6.