Xe⋯chalcogen aerogen bond. Effect of substituents and size of chalcogen atom

Literature Information

Publication Date 2020-02-03
DOI 10.1039/C9CP06648A
Impact Factor 3.676
Authors

Ruijing Wang, Haojie Liu, Qingzhong Li, Steve Scheiner


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Abstract

The aerogen bond between the Xe and chalcogen atoms in complexes pairing XeOF2 with R1YR2 is examined by ab initio calculations for Y = O, S, and Se. In addition to HYH, one or both H atoms are changed to F or methyl groups. The interaction energies are strong, varying between 21 and 54 kJ mol−1. The aerogen bond is composed of roughly half electrostatic attraction, with lesser contributions due to polarization and dispersion. Replacement of H by electron-withdrawing F on the base weakens the interaction, while electron releasing Me substituents have the opposite effect. Whereas the aerogen bonds are stronger for O than for S or Se for HYH, HYF, and MeYH, it is the heavier chalcogen atoms that form the stronger dimers for MeOF and MeOMe. These trends cannot be fully explained by molecular electrostatic potentials or by measures of charge transfer, nor are they entirely consistent with electron density topology.

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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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