Chow-shing Lam, Xi-Guang Wei, Yi PAN, Kai Chung Lau
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引用次数: 0
Abstract
The energetics of ionization and dissociation of benzylperoxy radical have been investigated using explicitly correlated coupled-cluster methods. The theoretical values for adiabatic ionization energy, 9.331 eV and cationic dissociation barrier, 0.155 eV, harmoniously predict the elusiveness of benzylperoxy radical in the contexts of photoionization and ion-molecule reaction. These properties make it stand out as an exception among unsaturated alkyl peroxy radicals, which typically undergo dissociative ionization. An in-depth scrutiny into the underlying electronic effects resulting in its elusiveness - predictably spanning photoionization mass spectrometry and ion-molecule reaction preparation - has profound implications, calling for a revised view of valence bond perspective. By employing localized intrinsic bond orbital (IBO) methods in the study of benzylperoxy radical cation, we present a case for re-introducing the Linnett double-quartet theory as the missing link between theoretical basis and intuitive mechanisms involving triplet species such as molecular oxygen.
期刊介绍:
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.