On the relative stabilities of H- and D-bonded water dimers

Abstract

The infrared spectra of water dimers formed from H2O, D2O, and HDO in krypton matrices have been recorded. Thermal equilibria between H- and D-bonded dimers have been studied. D bonding is preferred, and H-bonded dimers are approximately 60 cm−1 less stable than D-bonded dimers. The energy difference seems to be due to the higher value of the intermolecular out-of-plane H-bond shear vibration compared to the corresponding D-bond vibration.