On the directionality and non-linearity of halogen and hydrogen bonds

Literature Information

Publication Date 2014-08-14
DOI 10.1039/C4CP03376K
Impact Factor 3.676
Authors

J. Grant Hill, Anthony C. Legon


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Abstract

Benchmark quality structures and interaction energies have been produced using explicitly correlated coupled cluster methods for a systematic series of hydrogen and halogen bonded complexes: B⋯HCCH, B⋯HCl and B⋯ClF, with six different Lewis bases B. Excellent agreement with experimental structures is observed, verifying the method used to deduce the equilibrium deviation from collinearity of the intermolecular bond via rotational spectroscopy. This level of agreement also suggests that the chosen theoretical method can be employed when experimental equilibrium data are not available. The application of symmetry adapted perturbation theory reveals differences in the underlying mechanisms of interaction for hydrogen and halogen bonding, providing insights into the differences in non-linearity. In the halogen bonding case it is shown that the dispersion term is approximately equal to the overall interaction energy, highlighting the importance of choosing the correct theoretical method for this type of interaction.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

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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