High energy state interactions, energetics and multiphoto-fragmentation processes of HI

Literature Information

Publication Date 2022-02-15
DOI 10.1039/D1CP05714F
Impact Factor 3.676
Authors

Meng-Xu Jiang, Ágúst Kvaran


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Abstract

Mass resolved multiphoton ionization data for two-photon resonant excitations (REMPI) in the 69 000–79 000 cm−1 region were recorded for HI. REMPI spectra of fragment and molecular ions were derived from the data and analysed to obtain information relevant to the state interactions, energetics and photofragmentation processes of intermediate Rydberg and ion-pair states (HI**). Spectral perturbations observed as line shifts and intensity anomalies acted complementarily to demonstrate the effects of the state interactions. The interaction strength and character mixing of Rydberg states and Rydberg and ion-pair states of different interaction types and the states energetics were quantified by deperturbation analysis for the high energy region of 75 000–79 000 cm−1, which is dense in states. Energetics of new, not previously observed, Rydberg states, detected in the lower energy excitation region of 69 000–75 000 cm−1 was characterized by simulation calculations. Ion intensity borrowing effects, found in the spectra of interacting states, are evidence of alterations in two-photon transition probabilities due to state mixing. Based on variations in relative spectral line intensities the major photofragmentation processes involved are proposed. These involve one-photon excitation of the intermediate states (HI**) to form repulsive superexcited states (HI#) followed by autoionization, dissociation, photodissociation and photoionization processes to form ions. The importance of state interactions in multiphoton-fragmentation processes is evident from the work.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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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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