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 existence of a charge-transfer-to-solvent process when a KI contact ion pair (GP) dissolved in supercritical water (SCW) is excited by UV light was confirmed by use of electronic structure calculations applied to molecular dynamics trajectories. We observed similar behavior with fluid density as that found for the KI-CIP in supercritical ammonia (SCA); nevertheless, there are some distinct features in the two supercritical solvents. First, the effect of the solvent field due to the molecules lying beyond the first solvation shell is very different in SCW compared with that observed in SCA; in SCW it actually has a destabilizing effect over the ground and excited states. Second, our results for the thermodynamic behavior of the CIP indicate that SCA is better solvent than SCW for this species. The differences found can be attributed to the solvent molecules surrounding the CIP and bridging the two ions; they shield more efficiently the ion pair from long-range solvent effects in SCA. The different behavior is partially attributed to a stronger solvent-solvent interaction in SCW than in SCA. © 2008 American Chemical Society.

Registro:

Documento: Artículo
Título:Is ammonia a better solvent than water for contact ion Pairs?
Autor:Sciaini, G.; Marceca, E.; Fernández-Prini, R.
Filiación:INQUIMAE/DQIAQF, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Argentina
UAQ, Comisión Nacional de Energía Atómica, Argentina
Departments of Physics and Chemistry, Institute for Optical Sciences, University of Toronto, 80 St. George Street, Toronto, ON M5S 3H6, Canada
Palabras clave:Ammonia; Dissolution; Dynamics; Electric excitation; Electronic structure; Ions; Molecular dynamics; Quantum chemistry; Charge-transfer-to-solvent; Contact ion pairs; Destabilizing effects; Distinct features; Electronic-structure calculations; Excited-states; Fluid densities; Ion pairs; Molecular dynamics trajectories; Solvation shells; Solvent effects; Solvent molecules; Solvent-solvent interactions; Supercritical ammonia; Supercritical solvents; Supercritical water; U V light; Solvents
Año:2008
Volumen:112
Número:38
Página de inicio:11990
Página de fin:11995
DOI: http://dx.doi.org/10.1021/jp8042472
Título revista:Journal of Physical Chemistry B
Título revista abreviado:J Phys Chem B
ISSN:15206106
CODEN:JPCBF
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15206106_v112_n38_p11990_Sciaini

Referencias:

  • Sciaini, G., Marceca, E., Fernández-Prini, R., (2006) J. Phys. Chem. B, 110, pp. 8921-8923
  • Sciaini, G., Marceca, E., Fernández-Prini, R., (2006) Phys. Chem. Chem. Phys, 8, pp. 4839-4848
  • Sciaini, G.; Fernández-Prini, R.; Estrin, D. A.; Marceca, E. J. Chem. Phys. 2007, 126, 1745041-8; Sciaini, G., Marceca, E., Fernández-Prini, R., (2005) J. Phys. Chem. B, 109, pp. 18949-18955
  • Chen, H.Y., Sheu, W.S., (2000) J. Am. Chem. Soc, 122, pp. 7534-7542
  • Thompson, H., Wasse, J.C., Skipper, N.T., Rayanla, S., Brown, D.T., Soper, A.K., (2003) J. Am. Chem. Soc, 125, pp. 2572-2581
  • Impey, R.W., Klein, M.L., (1984) Chem Phys. Lett, 104, pp. 579-582
  • Berendsen, H.J.C., Grigera, J.R., Straatsma, T.P., (1987) J. Phys. Chem, 91, p. 6269
  • Weast, R.C., (1989) CRC Handbook of Chemistry and Physics, , CRC Press: Boca Raton, FL
  • Eisenberg, D., Kauzmann, W., (1969) The Structure and Properties of Water, , Oxford University Press: Oxford, U.K
  • Schütz, M., Brdarski, S., Widmark, P.-O., Lindh, R., Karlström, G., (1997) J. Chem Phys, 107, pp. 4597-4605
  • Starling, J., Schütz, M., Lindh, R., Kaiström, G., Widmark, P.-O., (2002) Mol. Phys, 100, pp. 3889-3399
  • Swiatla-Wojcik, D., (2007) Chem Phys, 342, pp. 260-266
  • Soper, A.K., Bruni, F., Ricci, M.A., (1997) J. Chem. Phys, 106, pp. 247-254
  • Franck, E.U., Structure of Water in Aqueous Solutions (1973) Proceedings of the International Symposium held in Marburg, Germany, July 1973, , Luck, W. A. P, Ed, Verlag Chemie: Berlin, Germany
  • Lemmon, W. W, Huber, M. L, McLinden, M. O. NIST Reference Fluid Thermodynamic and Transport Properties REFPROP, version 8.0; U.S. Department of Commerce, Gaithersburg, MD, 2007; Sciaini, G., Marceca, E., Fernández-Prini, R., (2005) J. Superem. Fluids, 35, pp. 106-110
  • Pitzer, K.S., Pabalan, R.T., (1988) Geochim. Cosmochim. Acta, 50, pp. 1445-1454
  • I is the ratio of the actual solublity in the supercritical fluid to that of the pure solid given by its vapor pressure; Bradforth, S.E., Jungwirth, P., (2002) J. Phys. Chem. A, 106, pp. 1286-1298
  • Case, D.A., Darden, T.A., Cheatham III, T.E., Simmerling, C.L., Wang, J., Duke, R.E., Luo, R., Kollman, P.A., (2004) AMBER 8, , University of California, San Francisco
  • Boulougouris, G.C., Economou, I.G., Theodorou, D.N., (1998) J. Phys. Chem B, 102, pp. 1029-1035
  • Hayward, T.H., Svishchev, I.M., (2001) Fluid Phase Equilib, 182, pp. 65-73
  • Frisch, M. J, Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Zakrzewski, V. G, Montgomery, J. A, Jr, Stratmann, R. E, Burant, J. C, Dapprich, S, Millam, J. M, Daniels, A. D, Kudin, K. N, Strain, M. C, Farkas, O, Tomasi, J, Barone, V, Cossi, M, Cammi, R, Mennucci, B, Pomelli, C, Adamo, C, Clifford, S, Ochterski, J, Petersson, G. A, Ayala, P. Y, Cui, Q, Morokuma, K, Malick, D. K, Rabuck, A. D, Raghavachari, K, Foresman, J. B, Cioslowski, J, Ortiz, J. V, Stefanov, B. B, Liu, G, Liashenko, A, Piskorz, P, Komaromi, I, Gomperts, R, Martin, R. L, Fox, D. J, Keith, T, Al-Laham, M. A, Peng, C. Y, Nanayakkara, A, Gonzalez, C, Challacombe, M, Gill, P. M. W, Johnson, B. G, Chen, W, Wong, M. W, Andres, J. L, Head-Gordon, M, Replogle, E. S, Pople, J. A. Gaussian 98; Gaussian Inc, Pittsburgh, PA, 1998; Blandamer, M.J., Fox, M.F., (1970) Chem. Rev, 70, pp. 59-93
  • Galabardes, J.F., Van Hare, J.R., Rogers, L.B., (1981) J. Chem. Eng. Data, 26, pp. 363-366
  • Amellini, F.J., Tester, J.W., (1992) Fluid Phase Equilib, 84, pp. 123-142
  • Gutkowski, K., Japas, M.L., Fernández-Prini, R., (1997) J. Chem. Thermodyn, 29, pp. 1077-1086
  • Chialvo, A.A., Simonson, J.M., (2003) J. Chem. Phys, 118, pp. 7921-7929

Citas:

---------- APA ----------
Sciaini, G., Marceca, E. & Fernández-Prini, R. (2008) . Is ammonia a better solvent than water for contact ion Pairs?. Journal of Physical Chemistry B, 112(38), 11990-11995.
http://dx.doi.org/10.1021/jp8042472
---------- CHICAGO ----------
Sciaini, G., Marceca, E., Fernández-Prini, R. "Is ammonia a better solvent than water for contact ion Pairs?" . Journal of Physical Chemistry B 112, no. 38 (2008) : 11990-11995.
http://dx.doi.org/10.1021/jp8042472
---------- MLA ----------
Sciaini, G., Marceca, E., Fernández-Prini, R. "Is ammonia a better solvent than water for contact ion Pairs?" . Journal of Physical Chemistry B, vol. 112, no. 38, 2008, pp. 11990-11995.
http://dx.doi.org/10.1021/jp8042472
---------- VANCOUVER ----------
Sciaini, G., Marceca, E., Fernández-Prini, R. Is ammonia a better solvent than water for contact ion Pairs?. J Phys Chem B. 2008;112(38):11990-11995.
http://dx.doi.org/10.1021/jp8042472