Insights for Light-Driven Molecular Devices from Ab Initio Multiple Spawning Excited-State Dynamics of Organic and Biological Chromophores

Abstract

We discuss the basic process of photoinduced isomerization as a building block for the design of complex, multifunctional molecular devices. The excited-state dynamics associated with isomerization is detailed through application of the ab initio multiple spawning (AIMS) method, which solves the electronic and nuclear Schrödinger equations simultaneously. This first-principles molecular dynamics approach avoids the uncertainties and extraordinary effort associated with fitting of potential energy surfaces and allows for bond rearrangement processes with no special input. Furthermore, the AIMS method allows for the breakdown of the Born-Oppenheimer approximation and thus can correctly model chemistry occurring on multiple electronic states. We show that charge-transfer states play an important role in photoinduced isomerization and argue that this provides an essential "design rule" for multifunctional devices based on isomerizing chromophores.