Electron correlation effects in the photoionization of CO and isoelectronic diatomic molecules
文献情報
A. Ponzi, N. Quadri, C. Angeli, P. Decleva
This paper investigates the first sigma satellite band, which is by far the most prominent, in the valence photoelectron spectra for a set of isoelectronic diatomic molecules: carbon monoxide, carbon monosulfide, carbon monoselenide, silicon monoxide and boron monofluoride. In particular, we analyze the effect of the electronic structure, with the change of the atomic pair along the row and column of the periodic table on the position of the satellite peak as well as on the related dynamical observables profiles. For this investigation, highly correlated calculations have been performed on the primary ionic states and the satellite band for all the molecules considered. Cross sections for the primary ionic states, calculated using Dyson orbitals, have been compared with those obtained with Hartree–Fock and Density Functional Theory to probe the impact of the correlation in the bound states on the photoionization observables. Limitations of a simple intensity borrowing mechanism clearly result from the analysis of the satellite state, characterized by different features with respect to the relevant primary states.
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掲載誌
Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.














