Comparison of the proton-transfer paths in hydrogen bonds from theoretical potential-energy surfaces and the concept of conservation of bond order III. O–H–O hydrogen bonds

Abstract

The quantum-mechanically derived reaction coordinates (QMRC) for the proton transfer in O–H–O hydrogen bonds have been derived from ab initio calculations of potential-energy surfaces. A comparison is made between the QMRC and the corresponding bond-order reaction coordinates (BORC) derived by applying the Pauling bond order concept together with the principle of conservation of bond order. In agreement with earlier results for N–H–N⁺ hydrogen bonds there is virtually perfect agreement between the QMRC and BORC curves for intermolecular O–H–O hydrogen bonds. For intramolecular O–H–O hydrogen bonds, the donor and acceptor parts of the molecule impose strong constraints on the O⋯O distance and the QMRC does not follow the BORC relation in the whole range. The neutron-determined proton positions are located close to the theoretically calculated potential-energy minima, and where the QMRC and the BORC curves coincide with each other. The results confirm the universal character of intermolecular hydrogen bonds: BORC is identical with QMRC and the proton can be moved from donor to acceptor keeping its valency equal to 1. The shape of PES for intramolecular hydrogen bonds is more complex as it is sensitive to the geometry of the molecule as well as of the hydrogen bridge.