Description of pnicogen bonding with the help of vibrational spectroscopy—The missing link between theory and experiment

The nature of the E⋯E′ pnicogen bond (E = N, P, As) in dimers such as H2FP⋯PH2F (1) and H3N⋯PHNO2 (2) can be described using vibrational spectroscopy in form of the calculated infrared and depolarized Raman scattering spectra. Utilizing the six calculated intermonomer frequencies, the corresponding local mode E⋯E′ stretching frequency and force constant are obtained, where the latter provides a unique measure of the E⋯E′ bond strength. Pnicogen bonding in 1 is relative strong (bond strength order n = 0.151) and covalent whereas pnicogen bonding in 2 is electrostatic (n = 0.047) because of a different bonding mechanism.