A Unified Strategy for the Chemically Intuitive Interpretation of Molecular Optical Response Properties

de Wergifosse, Marc [UCL] Grimme, Stefan [Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie der Universität Bonn, Bonn D-53115, Germany;]

Interpreting response properties such as the polarizability, optical rotation (OR), or hyperpolarizabilities is a complex task for which a uniform strategy would be desirable. We propose a response analysis procedure called the RespA approach with two interrelated schemes to describe molecular optical response properties in terms of natural response orbitals (NROs) and chemical fragment response for convenient elucidation of structure− optical)property relationships. These quantities can be easily extracted from the frequency-dependent perturbed one-electron transition/current density matrix obtained from any quantum mechanical response function calculation. NROs provide the most compact representation of the virtual excitations occurring in the (hyper)scattering process. It is decomposed in hole and electron NRO pairs providing a simple exciton picture. For a chemist, it is natural to interpret a property by decomposing it into functional groups or fragment contributions. In this spirit, the response is partitioned into on-site and between-site fragment responses, allowing a property mapping into real space. The new RespA procedure was implemented and tested at the simplified time-dependent density functional theory (sTD-DFT) level enabling calculations for large systems. The RespA strategy is a method-independent route for the understanding of a wide variety of response properties. We showcase how the chemically intuitive RespA approach extracts easily structure−property relationships for the particularly difficult case of OR. As examples, we demonstrate how to enhance the OR of [5]helicene and norbornenone, provide an analysis of the change of the OR observed for camphor and fenchone, and finally investigate the case of a (P,P)-bis-helicenic 2,2′-bipyridine chiroptical switch.