Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling

X-ray photoelectron spectra provide a wealth of information on the electronic structure. The extraction of molecular details requires adequate theoretical methods, which in case of transition metal complexes has to account for effects due to the multi-configurational and spin-mixed nature of the many-electron wave function. Here, the Restricted Active Space Self-Consistent Field method including spin-orbit coupling is used to cope with this challenge and to calculate valence and core photoelectron spectra. The intensities are estimated within the frameworks of the Dyson orbital formalism and the sudden approximation. Thereby, we utilize an efficient computational algorithm that is based on a biorthonormal basis transformation. The approach is applied to the valence photoionization of the gas phase water molecule and to the core ionization spectrum of the $\text{[Fe(H}_2\text{O)}_6\text{]}^{2+}$ complex. The results show good agreement with the experimental data obtained in this work, whereas the sudden approximation demonstrates distinct deviations from experiments

Valence and Core Photoelectron Spectra of Aqueous I3− from Multi-Reference Quantum Chemistry

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.Deutsche ForschungsgemeinschaftPeer Reviewe

Soft-X-Ray Absorption Spectroscopy and Ab Initio Calculations

Nonradiative decay channels in the L-edge fluorescence yield spectra from transition-metal–aqueous solutions give rise to spectral distortions with respect to x-ray transmission spectra. Their origin is unraveled here using partial and inverse partial fluorescence yields on the microjet combined with multireference ab initio electronic structure calculations. Comparing Fe2+, Fe3+, and Co2+ systems we demonstrate and quantify unequivocally the state- dependent electron delocalization within the manifold of d orbitals as one origin of this observation

ON THE 125TH ANNIVERSARY OF ACETYLSALICYLIC ACID

An experience of acetylsalicylic acid (ASA) clinical use since its synthesis in 1887 is highlighted. ASA modes of action and its position among the modern antiplatelet agents are considered. The evidence based clinical data on ASA treatment and the problem of antiplatelet therapy resistance are discussed. ASA interaction with other drugs and ASA pleiotropic effects are reviewe