AbstractHydrogen bonding interaction in hydrogen fluoride dimer has been investigated by quantum‐chemical calculation with 6‐311G**basis set at various mutual orientations. Atomic charges and charge transfer have been calculated by means of potential‐derived method, and decomposition of hydrogen bonding interaction has been executed. The calculation results show that there is a variation range for the energy‐stable orientations, the charge transfer in the range presents maximum value, and the charge transfer interaction plays a decisive role in the hydrogen