Ionization-induced π → H site-switching in phenol–CH4 complexes studied using IR dip spectroscopy

Literature Information

Publication Date 2013-11-13
DOI 10.1039/C3CP53533A
Impact Factor 3.676
Authors

Mitsuhiko Miyazaki, Akihiro Takeda, Matthias Schmies, Makoto Sakai, Kentaro Misawa, Shun-ichi Ishiuchi, François Michels, Klaus Müller-Dethlefs, Otto Dopfer, Masaaki Fujii


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Abstract

IR spectra of phenol–CH4 complexes generated in a supersonic expansion were measured before and after photoionization. The IR spectrum before ionization shows the free OH stretching vibration (νOH) and the structure of neutral phenol–CH4 in the electronic ground state (S0) is assigned to a π-bound geometry, in which the CH4 ligand is located above the phenol ring. The IR spectrum after ionization to the cationic ground state (D0) exhibits a red shifted νOH band assigned to a hydrogen-bonded cationic structure, in which the CH4 ligand binds to the phenolic OH group. In contrast to phenol–Ar/Kr, the observed ionization-induced π → H migration has unity yield for CH4. This difference is attributed to intracluster vibrational energy redistribution processes.

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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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