Solvent Dependence of the Electronic Structure of I- and I-3(-)

AuthorCount:9;
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- 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- explicitly depend on the details of the hydrogen bonding configurations of the solvent to the I- 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 I-3(-) and I-/I-3(-) 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- and I-3(-) can be rather different in nature.

Josefsson, IdaStockholms universitet,Fysikum(Swepub:su)ijose (author)
Ottosson, Niklas (author)
Öhrwall, GunnarLund University,Lunds universitet,MAX IV-laboratoriet,MAX IV Laboratory(Swepub:lu)maxl-goh (author)
Björneholm, Olle (author)
Siegbahn, Hans (author)
Hagfeldt, AndersUppsala universitet,Fysikalisk kemi(Swepub:uu)andehagf (author)
Odelius, MichaelStockholms universitet,Fysikum(Swepub:su)odelius (author)
Rensmo, Hakan (author)
Uppsala universitetFysikalisk kemi (creator_code:org_t)

In:Journal of Physical Chemistry B: American Chemical Society (ACS)118:11, s. 3164-31741520-61061520-5207

By the author/editor: Eriksson, Susann ...; Josefsson, Ida; Ottosson, Niklas; Öhrwall, Gunnar; Björneholm, Olle; Siegbahn, Hans; show more...; Hagfeldt, Anders; Odelius, Michael; Rensmo, Hakan; show less...

About the subject

By the university: Stockholm University; Uppsala University; Lund University

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