Electronic structure of norbornadiene and quadricyclane

TL;DR

This study investigates the electronic structures of norbornadiene and quadricyclane, introducing a new basis set and evaluating advanced methods to understand their photoisomerization, with implications for energy storage applications.

Contribution

A new custom basis set and a three-state valence model are introduced, enabling efficient and accurate simulations of photoexcited dynamics in these molecules.

Findings

Identified key valence states involved in isomerization.

Mapped the S$_1$/S$_0$ conical intersection.

Evaluated electronic structure methods for on-the-fly simulations.

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 {\it{on-the-fly}} simulations of photoexcited dynamics. The key valence states participating in the isomerisation reaction are investigated, specifically mapping the important S$_1$/S$_0$ 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 \textit{e.g}.\ energy-storage applications.