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Volumn 112, Issue 51, 2008, Pages 16908-16916

Guanine radical reaction processes: A computational description of proton transfer in X-irradiated 9-ethylguanine single crystals

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ENERGY; CRYSTALS; DIELECTRIC PROPERTIES; ELECTRON IRRADIATION; EXPERIMENTS; FLOW OF GASES; HYDROGENATION; IRRADIATION; MOLECULES; OXIDATION; PROTON IRRADIATION; PROTONS; REACTION KINETICS; SINGLE CRYSTALS;

EID: 58149149595     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp806262d     Document Type: Article
Times cited : (2)

References (36)
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    • +, respectively, indicate hydrogenation and protonation.
    • +, respectively, indicate hydrogenation and protonation.
  • 8
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    • Frisch, M. J. Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Montgomery, J. A, Jr, Vreven, T, Kudin, K. N, Burant, J. C, Millam, J. M, Iyengar, S. S, Tomasi, J, Barone, V, Mennucci, B, Cossi, M, Scalmani, G, Rega, N, Petersson, G. A, Nakatsuji. H, Hada, M, Ehara. M, Toyota, K, Fukuda, R, Hasegawa, J, Ishida. M, Nakajima, T, Honda, Y, Kitao, O, Nakai, H, Klene, M, Li, X, Knox, J. E, Hratchian, H. P, Cross, J. B, Bakken, V, Adamo, C; Jaramillo, J, Gomperts, R, Stratmann, R. E, Yazyev, O, Austin, A. J, Cammi, R, Pomelli, C; Ochterski, J. W, Ayala, P. Y, Morokuma, K, Voth. G. A, Salvador, P, Dannenberg, J. J, Zakrzewski, V. G, Dapprich, S, Daniels, A. D, Strain, M. C; Farkas, O, Malick, D. K, Rabuck, A. D, Raghavachari, K, Foresman, J. B, Ortiz, J. V, Cui, Q, Baboul, A. G, Clifford, S, Cioslowski, J, Stefanov, B. B, Liu, G, Liashenko, A, Piskorz, P, Komaromi, I, Martin, R. L, Fox, D. J, Keith, T
    • Frisch, M. J. Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji. H.; Hada, M.; Ehara. M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida. M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth. G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe. M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C; Pople, J. A. Gaussian 03, revision D.04; Gaussian, Inc.: Pittsburgh, PA, 2003.
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    • Born, M. Z. Phys. 1920, 1, 45.
    • (1920) Phys , vol.1 , pp. 45
    • Born, M.Z.1
  • 16
    • 84906411384 scopus 로고    scopus 로고
    • To obtain fully completed geometry optimizations in some cases, it was necessary to use the OPT=CALCALL option; accordingly, all geometries and frequencies for the individual-molecule cases were obtained with this approach.
    • To obtain fully completed geometry optimizations in some cases, it was necessary to use the "OPT=CALCALL" option; accordingly, all geometries and frequencies for the individual-molecule cases were obtained with this approach.
  • 20
    • 0343791148 scopus 로고    scopus 로고
    • We note that all absolute energies decreased with increasing ε, as expected. The increased relative energies shown in Table 1 for some molecules reflect the magnitude of their dipole moments in comparison to that of the parent. When placed within a dielectric, the energy of a neutral molecule will decrease in proportion to the square of its dipole moment Onsager's model of the dipole reaction field, Thus, with increasing ε, the parent's energy will decrease more rapidly than that of another neutral form with a smaller dipole moment: see: Onsager, L. J. Am. Chem. Soc. 1936, 58, 1486
    • We note that all absolute energies decreased with increasing ε, as expected. The increased relative energies shown in Table 1 for some molecules reflect the magnitude of their dipole moments in comparison to that of the parent. When placed within a dielectric, the energy of a neutral molecule will decrease in proportion to the square of its dipole moment (Onsager's model of the dipole reaction field). Thus, with increasing ε, the parent's energy will decrease more rapidly than that of another neutral form with a smaller dipole moment: see: Onsager, L. J. Am. Chem. Soc. 1936, 58, 1486.
  • 30
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    • We found a candidate for the transition structure connecting the pre- and post-transferred geometries of the reduction product in water that suggested forward and reverse barriers of 10.0 and 30.6 kJ/mol, respectively. These indicate a forward barrier that is quite low, 2.4 kcal/mol, Unfortunately, we were unable to confirm this as the correct transition structure because the IRC calculation did not go to completion
    • We found a candidate for the transition structure connecting the pre- and post-transferred geometries of the reduction product in water that suggested forward and reverse barriers of 10.0 and 30.6 kJ/mol, respectively. These indicate a forward barrier that is quite low (-2.4 kcal/mol). Unfortunately, we were unable to confirm this as the correct transition structure because the IRC calculation did not go to completion.


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