Bond Fragility Spectra for the Double Proton-Transfer Reaction in the Formic Acid-Type Dimers.

The newly developed method of fragility spectra for observation of bond breaking and formation upon a reaction has been applied to the canonical reaction series of the double proton transfer (DPT). Formic acid and its thio-analogues HCXYH (X, Y = O, S) have been chosen for the analysis. Very accurate linear correlations have been determined between the nondiagonal elements of the connectivity matrix, essential for the method, and the Wiberg bond orders for the corresponding bonds. Relation of the slope of this correlation to the global softness and to the atomic numbers of the bonded atoms has been proved, thus corroborating the c-DFT formula describing the fragility spectra. The electron density changes in bonds, as observed by the fragility spectra, are in harmony with the curvature diagrams reported by other authors.