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Origin of cooperativity in hydrogen bonding


The origin of non-additivity in hydrogen bonds (H-bonds), usually termed H-bond cooperativity, is investigated in H-bonded linear chains. It is shown that H-bond cooperativity originates solely from classical electrostatics. The latter is corroborated comparing the H-bond cooperativity in infinitely-long H-bonded hydrogen cyanide, 4-pyridone and formamide chains, assessed using density functional theory (DFT), against the strengthening of the dipole-dipole interaction upon the formation of an infinite chain of effective point-dipoles. It is found that magnitude of these effective point-dipoles is consequence of mutual polarization and additional effects beyond a polarizable point-dipole model. Nevertheless the effective point-dipoles are fully determined once a single H-bond is formed, indicating that quantum effects involved in H-bonding are circumscribed to nearest-neighbor interactions only; i. e. in a linear chain of H-bonds quantum effects do not contribute to the H-bond non-additivity. This finding is verified estimating cooperativity along the dissociation path of H-bonds in the infinite chains, using two empirical parameters that account for polarizability, together with DFT association energies and molecular dipoles of solely monomers and dimers.

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Publication details

The article was received on 16 Mar 2017, accepted on 15 May 2017 and first published on 15 May 2017

Article type: Paper
DOI: 10.1039/C7CP01695F
Citation: Phys. Chem. Chem. Phys., 2017, Accepted Manuscript
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    Origin of cooperativity in hydrogen bonding

    J. Nochebuena, C. Cuautli and J. Ireta, Phys. Chem. Chem. Phys., 2017, Accepted Manuscript , DOI: 10.1039/C7CP01695F

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