Kochetov Vladislav, Ahsan Md Sabbir, Hein Dennis, Wilkinson Iain, Bokarev Sergey I
Institut für Physik, Universität Rostock, Albert-Einstein-Str. 23-24, D-18059 Rostock, Germany.
Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, D-14109 Berlin, Germany.
Molecules. 2023 Jul 10;28(14):5319. doi: 10.3390/molecules28145319.
The I3- molecule is known to undergo substantial structural reorganization upon solvation by a protic solvent, e.g., water. However, the details of this process are still controversially discussed in the literature. In the present study, we combined experimental and theoretical efforts to disentangle this controversy. The valence (5p), N4,5 (4d), and M4,5 (3d) edge photoelectron spectra were measured in an aqueous solution and computed using high-level multi-reference methods. Our previous publication mainly focused on obtaining reliable experimental evidence, whereas in the present article, we focused primarily on theoretical aspects. The complex electronic structure of I3- requires the inclusion of both static and dynamic correlation, e.g., via the multi-configurational perturbation theory treatment. However, the resulting photoelectron spectra appear to be very sensitive to problems with variational stability and intruder states. We attempted to obtain artifact-free spectra, allowing for a more reliable interpretation of experiments. Finally, we concluded that the 3d Photoelectron Spectrum (PES) is particularly informative, evidencing an almost linear structure with a smaller degree of bond asymmetry than previously reported.
已知I3-分子在被质子溶剂（如水）溶剂化时会发生显著的结构重组。然而，这一过程的细节在文献中仍存在争议。在本研究中，我们结合了实验和理论方法来解决这一争议。在水溶液中测量了价（5p）、N4,5（4d）和M4,5（3d）边缘光电子能谱，并使用高水平的多参考方法进行了计算。我们之前的出版物主要集中在获得可靠的实验证据，而在本文中，我们主要关注理论方面。I3-的复杂电子结构需要同时考虑静态和动态关联，例如通过多组态微扰理论处理。然而，所得的光电子能谱似乎对变分稳定性和侵入态问题非常敏感。我们试图获得无伪影的能谱，以便对实验进行更可靠的解释。最后，我们得出结论，3d光电子能谱（PES）特别具有信息量，证明其结构几乎呈线性，键不对称程度比之前报道的要小。
