Navegar

Colección

Datos Estadísticas

Artículo

La versión final de este artículo es de uso interno. El editor solo permite incluir en el repositorio el artículo en su versión post-print. Por favor, si usted la posee enviela a
Consulte el artículo en la página del editor
Consulte la política de Acceso Abierto del editor

Abstract:

The study of the UV spectroscopic behaviour of alkali metal iodides dissolved in supercritical ammonia showed that two absorbing species contributed to the UV absorption of the solutions. The two species differed in the type of interaction of iodide with the cation, i.e. going from contact ion pairs to free iodide ion, the observed absorption band varied according to the species that prevailed as the solvent density (ρ1) changed. This experimental evidence was supplemented with molecular dynamics simulations and electronic structure calculations which showed that at very low ρ1 when the contact ion pair is the dominant species, a sudden change from the internal charge transfer photoexcitation route to a charge-transfer-to-solvent transition occurred. This finding emphasized the importance of solvation at very low ρ1 not only for the photoexcitation process, it also allows connecting the thermodynamic behaviour of the solutes in solution with that observed in their vapour phase. We have tried to draw a consistent picture of the available information of UV photoexcitation for iodides in vapour, in solution either forming contact ion pairs or present as free iodide ions, including their behaviour in small clusters of highly polar molecules. The importance of the cation has been clearly shown in this investigation. A relation between the photoexcited electron in contact ion pairs and the solvated electron of alkali metals in small NH3 clusters has been conjectured. © the Owner Societies 2006.

Registro:

Documento: Artículo
Título:Development of the charge-transfer-to-solvent process with increasing solvent fluid density: The effect of ion pairing
Autor:Sciaini, G.; Marceca, E.; Fernández-Prini, R.
Filiación:INQUIMAE-DQIAQF, Facultad de Cs. Exactas Y Naturales, Pabellón II, Buenos Aires, Argentina
Unidad de Actividad Química, Comisión Nacional de Energía Atómica, Av. Libertador 8250, Buenos Aires, Argentina
Palabras clave:ammonia; ion; potassium iodide; solvent; article; chemical structure; chemistry; computer simulation; pressure; temperature; volatilization; Ammonia; Computer Simulation; Ions; Models, Molecular; Potassium Iodide; Pressure; Solvents; Temperature; Volatilization
Año:2006
Volumen:8
Número:42
Página de inicio:4839
Página de fin:4848
DOI: http://dx.doi.org/10.1039/b608600b
Título revista:Physical Chemistry Chemical Physics
Título revista abreviado:Phys. Chem. Chem. Phys.
ISSN:14639076
CODEN:PPCPF
CAS:ammonia, 14798-03-9, 51847-23-5, 7664-41-7; potassium iodide, 7681-11-0; Ammonia, 7664-41-7; Ions; Potassium Iodide, 7681-11-0; Solvents
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14639076_v8_n42_p4839_Sciaini

Referencias:

  • Fox, M.A., (1992) Chem. Rev., 92, p. 365
  • Davidson, V.L., (2002) Biochemistry, 41, p. 14634
  • Kornyshev, A., Newton, M., Ulstrup, J., Sanderson, B., (2005) Chem. Phys., 319, p. 1
  • Martini, I.B., Barthel, E.R., Schwartz, B.J., (2001) Science, 293, p. 462
  • Blandamer, M.J., Fox, M.F., (1970) Chem. Rev., 70, p. 59
  • Smith, M., Symons, M.C.R., (1957) Discuss. Faraday Soc., 24, p. 206
  • Serxner, D., Dessent, C.E., Johnson, M.A., (1996) J. Chem. Phys., 105, p. 7231
  • Frischkorn, C., Weinkaufy, R., Neumark, D.M., (2000) Faraday Discuss., 115, p. 49
  • Elola, M.D., Laria, D., (2002) J. Chem. Phys., 117, p. 2238
  • Chen, H.-Y., Sheu, W.-S., (2000) J. Am. Chem. Soc., 122, p. 7534
  • Grégoire, G., Mons, M., Dimicoli, I., Dedonder-Lardeux, C., Jouvet, C., Martrenchard, S., Solgadi, D., (1999) J. Chem. Phys., 110, p. 1521
  • Grégoire, G., Mons, M., Dimicoli, I., Dedonder-Lardeux, C., Jouvet, C., Martrenchard, S., Solgadi, D., (2000) J. Chem. Phys., 112, p. 8794
  • Dedonder-Lardeux, C., Grégoire, G., Jouvet, C., Martrenchard, S., Solgadi, D., (2000) Chem. Rev., 100, p. 4023
  • Fernández-Prini, R., Japas, M.L., (1994) Rev. Chem. Soc., 23, p. 135
  • Sciaini, G., Marceca, E., Fernández-Prini, R., (2005) J. Supercrit. Fluids, 35, p. 106
  • Sciaini, G., Marceca, E., Fernández-Prini, R., (2005) J. Phys. Chem. B, 109, p. 18949
  • Haar, L., Gallagher, J.S., (1978) J. Phys. Chem. Ref. Data, 7, p. 635
  • Davidovits, P., Brodhead, D.C., (1967) J. Chem. Phys., 46, p. 2968
  • Hotop, H., Lineberger, W.C., (1985) J. Phys. Chem. Ref. Data, 14, p. 731
  • Fernández, D.P., Hefter, G., Fernández-Prini, R., (2001) J. Chem. Thermodyn., 33, p. 1309
  • Buback, M., Harder, W.D., (1977) Ber. Bunsen-Ges. Phys. Chem., 81, pp. 603-614. , 735
  • Hnizda, V.F., Kraus, C.A., (1949) J. Am. Chem. Soc., 71, p. 1565
  • Méndez De Leo, L., Bianchi, H., Fernández-Prini, R., (2005) J. Chem. Thermodyn., 37, p. 503
  • Eigen, M., Tamm, K., (1962) Z. Electrochem., 66, p. 107
  • Chialvo, A.A., Simonson, J.M., (2003) J. Chem. Phys., 118, p. 7921
  • Fernández-Prini Conductance In, R., (1973) Physical Chemistry of Organic Solvents, Eds., , A. K. Covington and T. Dickinson, Plenum Press, London
  • Sciaini, G., Marceca, E., Fernández-Prini, R., (2006) J. Phys. Chem. B, 110, pp. 8921-8923
  • Impey, W., Klein, M.L., (1984) Chem. Phys. Lett., 104, p. 579
  • Kindt, J.T., Schmuttenmaer, C.A., (1997) J. Chem. Phys., 106, p. 4389
  • Bradforth, S.E., Jungwirth, P., (2002) J. Phys. Chem. a, 106, p. 1286
  • Crawford, O.H., (1971) Mol. Phys., 20, p. 585
  • Lehr, L., Zanni, M.T., Frischkorn, C., Weinkauf, R., Neumark, D.M., (1999) Science, 284, p. 635
  • Berry In, R.S., (1979) Alkali Halide Vapors, Ed., , P. Davitovits, D. L. McFadden, Academic Press, New York
  • Foth, H.J., Polanyi, J.C., Telle, H.H., (1982) J. Phys. Chem., 86, p. 5027
  • Rose, T.S., Rosker, M.J., Zewail, A.H., (1989) J. Chem. Phys., 91, p. 7415
  • Cogin, G.E., Kimball, G.E., (1948) J. Chem. Phys., 16, p. 1035
  • Seward, T.M., Driesner In, T., (2004) Aqueous Systems at Elevated Temperatures and Pressures, Ed., , D. A. Palmer, R. Fernández-Prini and A. H. Harvey, Elsevier, Amsterdam, pp. 149-178
  • Cochran, H.D., Cummings, P.T., Karaborni, S., (1992) Fluid Phase Equilib., 71, pp. 1-16
  • Ciccotti, G., Ferrario, M., Hynes, J.T., Kapral, R., (1989) Chem. Phys., 129, pp. 241-251
  • Hertel, J.V., Hüglin, C., Nitsch, C., Schulz, C.P., (1991) Phys. Rev. Lett., 67, p. 1767
  • Steinbach, C., Buck, U., (2005) J. Chem. Phys., 122, p. 134301
  • Barnett, R.U., Landman, U., (1993) Phys. Rev. Lett., 70, p. 1775
  • Hashimoto, K., Morokuma, K., (1995) J. Am. Chem. Soc., 117, p. 4151

Citas:

---------- APA ----------
Sciaini, G., Marceca, E. & Fernández-Prini, R. (2006) . Development of the charge-transfer-to-solvent process with increasing solvent fluid density: The effect of ion pairing. Physical Chemistry Chemical Physics, 8(42), 4839-4848.
http://dx.doi.org/10.1039/b608600b
---------- CHICAGO ----------
Sciaini, G., Marceca, E., Fernández-Prini, R. "Development of the charge-transfer-to-solvent process with increasing solvent fluid density: The effect of ion pairing" . Physical Chemistry Chemical Physics 8, no. 42 (2006) : 4839-4848.
http://dx.doi.org/10.1039/b608600b
---------- MLA ----------
Sciaini, G., Marceca, E., Fernández-Prini, R. "Development of the charge-transfer-to-solvent process with increasing solvent fluid density: The effect of ion pairing" . Physical Chemistry Chemical Physics, vol. 8, no. 42, 2006, pp. 4839-4848.
http://dx.doi.org/10.1039/b608600b
---------- VANCOUVER ----------
Sciaini, G., Marceca, E., Fernández-Prini, R. Development of the charge-transfer-to-solvent process with increasing solvent fluid density: The effect of ion pairing. Phys. Chem. Chem. Phys. 2006;8(42):4839-4848.
http://dx.doi.org/10.1039/b608600b