The effect of hydrogen-bonding cooperativity on the strength and properties of σ-hole interactions: an ab initio study |
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| Authors: | Mehdi D Esrafili Mahshad Vakili |
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| Institution: | 1. Laboratory of Theoretical Chemistry, Department of Chemistry, University of Maragheh, Maragheh, Iran;2. Young Researchers and Elite Club, Miyaneh Branch, Islamic Azad University, Miyaneh, Iran |
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| Abstract: | Ab initio calculations at the MP2/aug-cc-pVTZ level of theory are performed to investigate the effect of hydrogen-bonding cooperativity on the strength and bonding properties of σ-hole interaction in linear FCl???(NCH)n=2–5, FHS???(NCH)n=2–5, FH2P???(NCH)n=2–5 and FH3Si???(NCH)n=2–5 clusters. It is found that the cooperative effects in the hydrogen-bonding tend to strengthen the σ-hole interaction. However, these effects are almost saturated in the larger clusters (n > 5). For a given cluster, the amount of bond contraction in FCl???(NCH)n is more important than other systems. A nice linear relationship is found between the σ-hole bond energies and absolute 15N chemical shieldings or spin–spin coupling constants across the σ-hole bond. |
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| Keywords: | Hydrogen bond halogen bond cooperativity MEP NMR |
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