We study alchemical atomic energy partitioning as a method to estimate atomization energies from atomic contributions which are defined in physically rigorous and general ways through use of the uniform electron gas as a joint reference.[1,2] We analyze quantitatively the relation between atomic energies and their local environment using a dataset of 1325 organic molecules. Atomic atomization energies are transferable across the various molecules, enabling the prediction of atomization energies with a mean absolute error of 23 kcal/mol - comparable to simple statistical estimates but potentially more robust given their grounding in the physics-based decomposition scheme. A comparative analysis with other decomposition methods highlights its sensitivity to electrostatic variations, underlining its potential as representation of the environment as well as in studying processes like diffusion in solids characterized by significant electrostatic shifts.
Michael J. Sahre