The structure, properties, and nature of HArF–benzene complex: Redshift and blueshift of Ar–H stretch frequency and rare gas atomic number dependence of hydrogen bonds

Ab initio calculations have been performed for the complexes of benzene with HArF, HKrF, and HXeF. The computed results indicate that the complexes of benzene–HArF exist in different conformations and among them those with π-hydrogen bonds are the more stable than those with C–H⋯F hydrogen bonds. Interestingly, the Ar–H stretching frequency is redshifted in the more stable isomer and blueshifted in the less stable form. The Ng (Ng = Ar, Kr, and Xe) atomic number dependence of the Ng–H⋯π and C–H⋯F hydrogen bonds has been explored. The result indicates that the strength of Ng–H⋯π and C–H⋯F hydrogen bonds is weakened with the increase of Ng atomic number. Natural bond orbital analysis has been performed to understand the interaction nature, frequency shift of H–Ng stretch, and dependence of Ng–H⋯π and C–H⋯F hydrogen bonds on the Ng atomic number.

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► We studied two types of isomers for HArF–benzene complex.
► One is combined by a π hydrogen bond.
► The other is combined with a C–H hydrogen bond.
► A red shift is observed for the Ar–H stretch vibration in the π hydrogen bond.
► A blue shift is observed for the Ar–H stretch vibration in the C–H hydrogen bond.