The spectroscopy of Rydberg to Rydberg transitions in I2 and Br2 investigated by vibrationally induced autoionization
Literature Information
Martin C. R. Cockett, David A. Beattie, Neil A. Macleod, Kenneth P. Lawley, Trevor Ridley, Robert J. Donovan
Dipole-allowed transitions from vibrationally selected members of the lowest nd Rydberg state cluster in I2 (n = 5) and Br2 (n = 4) to autoionizing Rydberg series based on vibrationally excited states of the core are investigated. The photoelectron production spectrum is recorded using delayed field extraction to detect free electrons released by autoionization with up to a few hundred cm−1 of energy that are subsequently trapped for ∼1μs in the plasma formed at the laser focus. The final state principal quantum numbers typically range from n ∼ 20–35 and both p and f series can be identified. When one of these core-excited Rydberg state energies coincides with the ionization threshold of a lower vibrational state to within a few cm−1, a marked increase in the ZEKE-PFI signal is observed, leading to non-Franck–Condon behaviour. Probing the same Rydberg states based on the spin–orbit excited core reveals preferential autoionization by electron exchange rather than by vibronic coupling in the p series.
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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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