The Energy Components of the Extended Transition State Energy Decomposition Analysis Are Path Functions: the Case of Water Tetramer

Abstract

A recent paper (Phys. Chem. Chem. Phys. 2020, 22:22459) shows that the energy components of the extended transition state energy decomposition analysis (ETS-EDA) are path functions, and, therefore, they are not uniquely defined. In this work, we apply the ETS-EDA to analyze all possible dissociation paths of the water tetramer to four free water molecules. Our results confirm that the energy components of the ETS-EDA are path functions. However, they also show that differences among energy components obtained for the different paths are relatively small, and, therefore, we conclude that the information obtained from an ETS-EDA can be used to discuss the nature of chemical bonds and analyze the origin of isomerization energies and energy barriers. However, if a given process can be attained by means of different and chemically reasonable paths, we recommend to perform the ETS-EDA of a given reaction for all different paths to confirm that energy components of the ETS-EDA do not differ very much from one path to another