Isomer-selective infrared spectroscopy of the cationic trimethylamine dimer to reveal its charge sharing and enhanced acidity of the methyl groups
Literature Information
Yuichiro Nakayama, Naohiko Mikami, Asuka Fujii
Infrared predissociation spectroscopy of the trimethylamine dimer cation generated by the vacuum-ultraviolet photoionization is isomer-selectively carried out by monitoring two main fragment channels, protonated trimethylamine and the trimethylamine monomer cation. The spectral carriers monitored by these two channels are assigned to different isomers of the trimethylamine dimer cation. One is the charge-shared (hemibond) structure, in which the positive charge is intermolecularly delocalized over the dimer through the interaction between the nonbonding orbitals of the nitrogen atoms. In the other isomer, a proton of a methyl group in the ionized moiety is intermolecularly transferred to the nitrogen atom of the neutral moiety and is shared between the carbon and nitrogen atoms. The latter isomer shows that the methyl groups of cationic trimethylamine are highly acidic. This example demonstrates characteristic properties of radical cations with alkyl groups.
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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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