Revealing photofragmentation dynamics through interactions between Rydberg states: REMPI of HI as a case study
Literature Information
Helgi Rafn Hróðmarsson, Ágúst Kvaran
High energy regions of molecular electronic states are largely characterized by the nature and involvement of Rydberg states. Whereas there are a number of observed dynamical processes that are due to interactions between Rydberg and valence states, reports on the corresponding effect of Rydberg–Rydberg state interaction in the literature are scarce. Here we report a detailed characterization of the effects of interactions between two Rydberg states on photofragmentation processes, for a hydrogen halide molecule. Perturbation effects, showing as rotational line shifts, intensity alterations and line-broadenings in REMPI spectra of HI, for two-photon resonance excitations to the j3Σ−(0+; v′ = 0) and k3Π1(v′ = 2) Rydberg states, are analyzed. The data reveal pathways of further photofragmentation processes involving photodissociation, autoionization and photoionization affected by the Rydberg–Rydberg state interactions as well as the involvement of other states, close in energy. Detailed mechanisms of the involved processes are proposed.
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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.











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