Electronic structure of norbornadiene and quadricyclane†

Abstract

The ground and excited state electronic structure of the molecular photoswitches quadricyclane and norbornadiene is examined qualitatively and quantitatively. A new custom basis set is introduced, optimised for efficient yet accurate calculations. A number of advanced multi-configurational and multi-reference electronic structure methods are evaluated, identifying those sufficiently accurate and efficient to be used in on-the-fly simulations of photoexcited dynamics. The key valence states participating in the isomerisation reaction are investigated, specifically mapping the important S₁/S₀ conical intersection that governs the non-radiative decay of the excited system. The powerful yet simple three-state valence model introduced here provides a suitable base for future computational exploration of the photodynamics of the substituted molecules suitable for e.g. energy-storage applications.