Solvation and the excited-state tautomerization of 7-azaindole and 1-azacarbazole: Computer simulations in water and alcohol solvents

Journal of Physical Chemistry A

Volumn 102, Issue 22, 1998, Pages 3860-3876

  Mente, S ^a   Maroncelli, M ^a  

^a PENNSYLVANIA STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000431110     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp980771d     Document Type: Article

References (69)

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25. In ref 16 Petrich and co-workers suggested that the differences in reaction rates of 7-AI in different alcohols may be due to differences in the acidity of different alcohols affecting the actual proton-transfer step. In our view, the fact that the isotope effect does not vary substantially over a range of alcohol solvents makes this interpretation seem unlikely.
26. BT/h) factor here.
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29. Under these conditions tert-butyl alcohol is actually a solid (mp, 25.5 °C); however, no behavior signaling an incipient phase transition was observed in this case.
30. See, for example, the following. Computer Simulation of Liquids; Allen, M. P., Tildesley, D. J., Eds.; Oxford, 1987.
31. HO) function, which is somewhat unusual, was arrived at by trial and error. The more commonly used harmonic constraint potentials were not as useful for our purposes.
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33. The semiempirical calculations performed with the following program. AMPAC, Version 5.0; SemiChem: Shawnee, KS, 1995.
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35. Ab initio calculations were performed with the Gaussian94 program. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; 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. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian 94, Revision B.1; Gaussian, Inc.: Pittsburgh, PA, 1995. Charges fit according to the Merz-Singh-Kollman scheme, Singh, U. C.; Kollman. P. A. J. Comput. Chem. 1984, 5, 129. Besler, B. H.; Merz, K. M.; Kollman, P. A. J. Comput. Chem. 1990, 11, 431.
36. Ab initio calculations were performed with the Gaussian94 program. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; 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. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian 94, Revision B.1; Gaussian, Inc.: Pittsburgh, PA, 1995. Charges fit according to the Merz-Singh-Kollman scheme, Singh, U. C.; Kollman. P. A. J. Comput. Chem. 1984, 5, 129. Besler, B. H.; Merz, K. M.; Kollman, P. A. J. Comput. Chem. 1990, 11, 431.
37. Ab initio calculations were performed with the Gaussian94 program. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; 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. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian 94, Revision B.1; Gaussian, Inc.: Pittsburgh, PA, 1995. Charges fit according to the Merz-Singh-Kollman scheme, Singh, U. C.; Kollman. P. A. J. Comput. Chem. 1984, 5, 129. Besler, B. H.; Merz, K. M.; Kollman, P. A. J. Comput. Chem. 1990, 11, 431.
38. See the examples and discussion in the following. Reynolds, L.; Gardecki, J. A.; Frankland, S. J. V.; Horng, M. L.; Maroncelli, M. J. Phys. Chem. 1996, 100, 10337.
39. We have used MC simulations to compute the association constants for 1:1 complexes between these solutes and a number of complexing partners for which there is dilute solution data available. We find reasonably good agreement using the same solute - solvent potentials employed here. [Mente, S.; Moog, R. S.; Maroncelli, M. Manuscript in preparation.]
40. 30 using key word "CI=12" specifying use of an CI calculation of 100 microstates formed from selected excitations among the 12 molecular orbitals bracketing the HOMO-LUMO gap.
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57. This need not be the case. One might have imagined the cyclic form to be a local minimum in the solvation free energy surface, in which case the reactive geometry once formed would persist for some time. However, in none of the systems studied have we found evidence of the cyclic geometry being at a local minimum in free energy.
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60. ‡ using this criterion.
61. This manner of charge variation was motivated by ab initio calculations, which show that in different alkyl alcohols the H atom charge is nearly constant while the O atom charge and the group to which it is attached account for most of the variations observed.
62. This feature of the TFE model is disturbing since empirically TFE is found to be a much stronger hydrogen bond donor than methanol. See for example, the following. Abraham, M. H. Chem. Soc. Rev. 1993, 22, 73. Marcus, Y. J. Solution Chem. 1991, 20, 929.
63. This feature of the TFE model is disturbing since empirically TFE is found to be a much stronger hydrogen bond donor than methanol. See for example, the following. Abraham, M. H. Chem. Soc. Rev. 1993, 22, 73. Marcus, Y. J. Solution Chem. 1991, 20, 929.
64. PT ≈ 50 fs.
65. Nakajima, A.; Hirano, M.; Hasumi, R.; Kaya, K.; Watanabe, H.; Carter, C. C.; Williamson, J. M.; Miller, T. L. J. Phys. Chem. A 1997, 101, 392.
66. 21
67. Based on the data in ref 20 over the temperature range 203-323 K. Uncertainties listed here are ±2 standard deviations.
68. Mente, S.; Maroncelli, M. Work in progress.
69. Reynolds, L. E.; Maroncelli, M. To be published.