Articles written in Journal of Chemical Sciences

    • Intramolecular hydrogen bond: Can it be part of the basis set of valence internal coordinates in normal mode analysis?

      Sarvesh Kumar Pandey Prasanta Das Puspendu K Das Elangannan Arunan Sadasivam Manogaran

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      It has been shown earlier1 that the relaxed force constants (RFCs) could be used as a measure of bond strength only when the bonds form a part of the complete valence internal coordinates (VIC) basis. However, if the bond is not a part of the complete VIC basis, its RFC is not necessarily a measure of bond strength. Sometimes, it is possible to have a complete VIC basis that does not contain the intramolecular hydrogen bond (IMHB) as part of the basis. This means the RFC of IMHB is not necessarily a measure of bond strength. However, we know that IMHB is a weak bond and hence its RFC has to be a measure of bond strength. We resolve this problem of IMHB not being part of the complete basis by postulating `equivalent’ basis sets where IMHB is part of the basis at least in one of the equivalent sets of VIC. As long as a given IMHB appears in one of the equivalent complete VIC basis sets, its RFC could be used as a measure of bond strength parameter.

    • Why are Hydrogen Bonds Directional?


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      The recent IUPAC recommendation on the definition of hydrogen bonding points out that directionality is a defining characteristic of a hydrogen bond and the angle ∠X-H-Y is generally linear or 180◦. It also suggests that the X-H· · ·Y angle be greater than 110◦ for an interaction to be characterized as a hydrogenbond but does not provide any rationale for the same. This article reports a rationale for limiting the angle, based on the electron density topology using the quantum theory of atoms in molecules. Electron density topology for common hydrogen bond donors HF, HCl, HBr, HNC, HCN and HCCH are reported in this work. These calculations lead to an interesting observation that the atomic basins of H atom in all these donor molecules are limited justifying the restriction of hydrogen bond angle. Moreover, similar analysis on some hydrogen bonded complexes confirms that beyond this angle the acceptor atom Y starts interacting with the atomic basin on X. However, conclusions based on bond lengths and angles have to be treated with care and as the IUPAC recommendation points out that independent ‘evidence for bond formation’ in every case is important.

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