4d orbital8/1/2023 8–12 These studies all demonstrate how the structure of the molecular ion and, in particular, its degree of nuclear asymmetry can be directly correlated with the varied strength of solvent–solute interaction in different solutions. Here, a crucial point is to predict and identify spectral signatures that are characteristic and yet readily detected in measurements, in addition to assigning and rationalizing the spectral features to facilitate an understanding of the underlying chemical and spectroscopic mechanisms.Īs an important component in dye-sensitized solar cells, the electronic, structural and dynamic properties of I 3 − in solution have been studied in great detail both with experimental 5–7 and theoretical methods. 4 Robust and detailed analysis of such experiments, however, often demands comparison to accurate theoretical simulations of spectra. electrolyte solutions 2,3 and at liquid interfaces. 1 With the development of new delivering systems such as liquid jets combined with improved X-ray sources, XPS studies in the liquid phase have become increasingly viable to investigate the effects of solute–solvent interactions in e.g. 1 Introduction Photoelectron spectroscopy is one of the most powerful and widely applied experimental methods for studies of electronic structure of matter, which in the X-ray regime (XPS), by targeting of core-levels, constitutes an element-specific local probe around distinct atomic sites in molecules and complex materials. The relative intensity of shake-up and main features of the I 4d XPS spectrum could therefore serve as a simplified experimental observable of structural asymmetry, complementary to changes in the shape of the main spectral features. ![]() In particular, it demonstrates how the nuclear asymmetry directly causes an increase of shake-up intensity. ![]() The analysis based on the occupation numbers of natural orbitals allowed to predict and rationalize the spectral fingerprints of solvent-induced nuclear asymmetry. A combination of multi-configurational restricted active space calculations with a Dyson orbital formalism has been applied for accurate simulations of 4d photo-electron spectra of the I 3 − molecular ion.
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