Symmetry and 1H NMR chemical shifts of short hydrogen bonds: impact of electronic and nuclear quantum effects
文献情報
Shengmin Zhou, Lu Wang
Short hydrogen bonds (SHBs), which have donor and acceptor separations below 2.7 Å, occur extensively in small molecules and proteins. Due to their compact structures, SHBs exhibit prominent covalent characters with elongated Donor–H bonds and highly downfield (>14 ppm) 1H NMR chemical shifts. In this work, we carry out first principles simulations on a set of model molecules to assess how quantum effects determine the symmetry and chemical shift of their SHBs. From simulations that incorporate the quantum mechanical nature of both the electrons and nuclei, we reveal a universal relation between the chemical shift and the position of the proton in a SHB, and unravel the origin of the observed downfield spectral signatures. We further develop a metric that allows one to accurately and efficiently determine the proton position directly from its 1H chemical shift, which will facilitate the experimental examination of SHBs in both small molecules and biological macromolecules.
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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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