Solvent Dependence of the Electronic Structure of I鈥?/sup> and I3鈥?/sup>

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• 作者：Susanna K. Eriksson ; Ida Josefsson ; Niklas Ottosson ; Gunnar 脰hrwall ; Olle Bj枚rneholm ; Hans Siegbahn ; Anders Hagfeldt ; Michael Odelius ; H氓kan Rensmo
• 刊名：Journal of Physical Chemistry B
• 出版年：2014
• 出版时间：March 20, 2014
• 年：2014
• 卷：118
• 期：11
• 页码：3164-3174
• 全文大小：427K
• 年卷期：v.118,no.11(March 20, 2014)
• ISSN：1520-5207

文摘

We present synchrotron-based I4d photoelectron spectroscopy experiments of solutions from LiI and LiI₃ in water, ethanol, and acetonitrile. The experimentally determined solvent-induced binding energy shifts (SIBES) for the monatomic I^{鈥?/sup> anion are compared to predictions from simple Born theory, PCM calculations, as well as multiconfigurational quantum chemical spectral calculations from geometries obtained through molecular dynamics of solvated clusters. We show that the SIBES for I鈥?/sup> explicitly depend on the details of the hydrogen bonding configurations of the solvent to the I鈥?/sup> and that static continuum models such as the Born model cannot capture the trends in the SIBES observed both in experiments and in higher-level calculations. To extend the discussion to more complex polyatomic anions, we also performed experiments on I₃鈥?/sup> and I鈥?/sup>/I₃鈥?/sup> mixtures in different solvents and the results are analyzed in the perspective of SIBES. The experimental SIBES values indicate that the solvation effects even for such similar anions as I鈥?/sup> and I₃鈥?/sup> can be rather different in nature.}