Observation of the hemibond formation in (H2O-Arn)+ radical cation clusters by electronic spectroscopy and ion imaging technique

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2025-03-28 DOI:10.1039/d5cp01001b

Mizuhiro Kominato, Takumi Koshiba, Fuminori Misaizu, Asuka Fujii

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引用次数: 0

Abstract

The hemibond is a non-classical covalent bond formed by the overlap of non-bonding orbitals of a radical (cation) and a closed-shell molecule. For (H₂O-Ar_n)⁺ radical cation clusters, competition between the hemibonded type and hydrogen-bonded (H-bonded) type isomers has been discussed on the basis of infrared spectroscopy and theoretical computations. It has been commonly recognized that the H-bonded type is predominant, while the coexistence of the hemibonded type remains a topic of debate. Hemibonded species are known to exhibit very strong electronic transitions in the ultraviolet and/or visible (UV-Vis) region, which are marker bands for hemibond formation. In this study, we performed electronic spectroscopy and photofragment ion imaging experiments on (H₂O-Ar_n)⁺ to observe the hemibond formation between H₂O⁺ and Ar. The observed spectra of (H₂O-Ar_n)⁺ (n = 1-3) exhibit absorption in the UV and visible regions. A comparison with quantum chemical calculations suggests the coexistence of the hemibonded type in (H₂O-Ar_n)⁺ (n = 1 and 2). In addition, the photofragment ion imaging experiment on (H₂O-Ar)⁺ showed an angular distribution attributed to the absorption of the hemibonded type, providing firm experimental evidence of the coexistence of the hemibonded type.

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来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

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.