The Connectivity Matrix: A Toolbox for Monitoring Bonded Atoms and Bonds

The concept of a connectivity matrix, essential for the reaction fragility (RF) spectra technique for monitoring electron density evolution in a chemical reaction, has been supported with a novel formulation for the diagonal matrix elements; their direct link to the electron density function ρ(r) has been demonstrated. By combining the concept with the atomization energy of a system, the separation of the potential energy into atomic and/or bond contributions has been achieved. The energy derivative diagrams for atoms and bonds that are variable along a reaction path provide new insight into the reaction mechanism. Diagonalization of the connectivity matrix resulted in the eigenvectors that provide information on a role of individual atoms in the development of structural changes along a reaction path.