The effect of hydrogen-bonding cooperativity on the strength and properties of σ-hole interactions: an ab initio study

2017-03-09T17:29:50Z (GMT) by Mehdi D. Esrafili Mahshad Vakili

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=25, FHS⋅⋅⋅(NCH)n=25, FH2P⋅⋅⋅(NCH)n=25 and FH3Si⋅⋅⋅(NCH)n=25 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.