Generalizing energy decomposition analysis to response properties to inform expedited predictive models

Abstract

We present a generalization of energy decomposition analysis (gEDA) for the analysis of molecular response properties, such as polarizabilities. The gEDA approach analyzes the interplay between molecular moieties in terms of chemically intuitive contributions to the observable response property, such as inter-fragment polarization or charge delocalization. The fragment-localized formulation enables one to develop expedited predictive models of response properties based on single-fragment and fragment-pair contributions. We present numerical tests on thiophene oligomers and demonstrate how to harness gEDA to develop a bottom-up understanding of response properties in terms of communicating molecular moieties. We demonstrate how gEDA can be used to develop predictive models for response properties such as the polarizability to provide insights into structure-function relations and to reduce the computational scaling by at least two orders of magnitude compared to canonical calculations, while preserving numerical accuracy.