Interaction of CHX3 (X = F, Cl, Br) with HNO induces remarkable blue shifts of both C–H and N–H bonds

Literature Information

Publication Date 2008-12-15
DOI 10.1039/B816112G
Impact Factor 3.676
Authors

Tran Thanh Hue, Minh Tho Nguyen


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Abstract

The hydrogen-bonded complexes formed from interaction of trihalomethanes CHX3 (X = F, Cl, Br) with nitrosyl hydride HNO were studied using ab initio MO calculations at the second-order perturbation theory (MP2/6-311++G(d,p)). Each interaction contains at least five separate equilibrium structures. Calculated binding energies range from 4 to 8 kJ mol−1 with both ZPE and BSSE corrections. While CHBr3 leads to the most stable complexes with HNO, CHF3 forms the least stable counterparts. The strength of complexes thus tends to increase from F to Cl to Br, which is consistent with a decrease of deprotonation enthalpy of the corresponding C–H bonds. It is remarkable that all the C–H and N–H bonds are shortened upon complexation, giving rise to an increase of their stretching frequencies. A blue shift is thus observed for the N–H bonds of the type N–H⋯X (X = F, Cl, Br); such a contraction of the covalent N–H bond is extremely rare.

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Front/Back Matter

DOI: 10.1039/C6PY90082H

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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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