Electronic spectroscopy of I(2)-Xe complexes in solid Krypton

The Journal of Chemical Physics
Eero HulkkoMika Pettersson

Abstract

In the present work, we have studied ion-pair states of matrix-isolated I(2) with vacuum-UV absorption and UV-vis-NIR emission, where the matrix environment is systematically changed by mixing Kr with Xe, from pure Kr to a more polarizable Xe host. Particular emphasis is put on low doping levels of Xe that yield a binary complex I(2)-Xe, as verified by coherent anti-Stokes Raman scattering (CARS) measurements. Associated with interaction of I(2) with Xe we can observe strong new absorption in vacuum-UV, redshifted 2400 cm(-1) from the X → D transition of I(2). Observed redshift can be explained by symmetry breaking of ion-pair states within the I(2)-Xe complex. Systematic Xe doping of Kr matrices shows that at low doping levels, positions of I(2) ion-pair emissions are not significantly affected by complexation with Xe, but simultaneous increase of emissions from doubly spin-excited states indicates non-radiative relaxation to valence states. At intermediate doping levels ion-pair emissions shift systematically to red due to change in the average polarizability of the environment. We have conducted spectrally resolved ultrafast pump-probe ion-pair emission studies with pure and Xe doped Kr matrices, in order to reveal the influ...Continue Reading

References

Feb 19, 2002·Chemical Reviews·V. A. Apkarian, N. Schwentner
Jul 23, 2004·The Journal of Chemical Physics·Z BiharyV A Apkarian
Nov 10, 2006·The Journal of Chemical Physics·Tiina KiviniemiMika Pettersson
May 2, 2008·The Journal of Chemical Physics·Yukio NakanoTakashi Ishiwata
May 21, 2008·The Journal of Physical Chemistry. a·Tiina KiviniemiMika Pettersson
Apr 2, 2009·The Journal of Chemical Physics·Trevor RidleyRobert J Donovan
Mar 7, 2005·Physical Chemistry Chemical Physics : PCCP·Michael KaravitisV Ara Apkarian
Oct 8, 2009·Physical Chemistry Chemical Physics : PCCP·G HancockS Taylor
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