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Abstract:

The UV-spectroscopic behavior of KI dissolved in supercritical ammonia enabled us to identify two species that contribute to the optical absorption depending on the fluid density ρ1 and the temperature T. At low ρ1 and high T, contact ion pairs (CIPs) prevail, while at high density of ammonia, solvent separated ion pairs (SSIPs) and free iodide ions dominate the optical absorption of the solute. The features of the electron excitation process depend on the state of the K+I- species present. Starting with isolated KI in the vapor, where the process is an interionic charge transfer, when the CIP becomes solvated the UV absorption shifts strongly to the blue. As ρ1 increases, the amounts of SSIP and of free iodide increase progressively and their electronic excited states become those characteristic of the charge-transfer-to-solvent process. This study suggests there is a strong influence of the cation on the electronic transition of dissolved iodide when it is forming CIPs. Moreover, the fact that K+-NH3 interaction is much larger than that of I --NH3 suggests that the electronic photoinduced excited state of CIPs is similar to the ground state observed for alkali metals in NH3 clusters. © 2005 American Chemical Society.

Registro:

Documento: Artículo
Título:Influence of ion pairing on the UV-spectral behavior of KI dissolved in supercritical NH3: From vapor phase to condensed liquid
Autor:Sciaini, G.; Marceca, E.; Fernández-Prini, R.
Filiación:INQUIMAE-DQIAQF, Facultad Cs. Exactas y Naturales, Pabellon II, Buenos Aires, Argentina
Unidad Actividad Química, Comisión Nacional Energía Atómica, Av. Libertador 8250, Buenos Aries, Argentina
Palabras clave:Charge transfer; Density (specific gravity); Dissolution; Ground state; Light absorption; Positive ions; Ultraviolet radiation; Excited states; Fluid density; Ion pairing; Supercritical ammonia; Supercritical fluids
Año:2005
Volumen:109
Número:40
Página de inicio:18949
Página de fin:18955
DOI: http://dx.doi.org/10.1021/jp053446g
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_v109_n40_p18949_Sciaini

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Citas:

---------- APA ----------
Sciaini, G., Marceca, E. & Fernández-Prini, R. (2005) . Influence of ion pairing on the UV-spectral behavior of KI dissolved in supercritical NH3: From vapor phase to condensed liquid. Journal of Physical Chemistry B, 109(40), 18949-18955.
http://dx.doi.org/10.1021/jp053446g
---------- CHICAGO ----------
Sciaini, G., Marceca, E., Fernández-Prini, R. "Influence of ion pairing on the UV-spectral behavior of KI dissolved in supercritical NH3: From vapor phase to condensed liquid" . Journal of Physical Chemistry B 109, no. 40 (2005) : 18949-18955.
http://dx.doi.org/10.1021/jp053446g
---------- MLA ----------
Sciaini, G., Marceca, E., Fernández-Prini, R. "Influence of ion pairing on the UV-spectral behavior of KI dissolved in supercritical NH3: From vapor phase to condensed liquid" . Journal of Physical Chemistry B, vol. 109, no. 40, 2005, pp. 18949-18955.
http://dx.doi.org/10.1021/jp053446g
---------- VANCOUVER ----------
Sciaini, G., Marceca, E., Fernández-Prini, R. Influence of ion pairing on the UV-spectral behavior of KI dissolved in supercritical NH3: From vapor phase to condensed liquid. J Phys Chem B. 2005;109(40):18949-18955.
http://dx.doi.org/10.1021/jp053446g