Control Mechanisms of Photoisomerization in Protonated Schiff Bases

Abstract

We performed ab initio excited-state molecular dynamics simulations of a gas-phase photoexcited protonated Schiff base (C₁–N₂═C₃–C₄═C₅–C₆) to search for control mechanisms of its photoisomerization. The excited molecule twists by ∼90° around either the N₂C₃ bond or the C₄C₅ bond and relaxes to the ground electronic state through a conical intersection with either a trans or cis outcome. We show that a large initial distortion of several dihedral angles and a specific normal vibrational mode combining pyramidalization and double-bond twisting can lead to a preferential rotation of atoms around the C₄C₅ bond. We also show that selective pretwisting of several dihedral angles in the initial ground state thermal ensemble (by analogy to a protein pocket) can significantly increase the fraction of photoreactive (cis → trans) trajectories. We demonstrate that new ensembles with higher degrees of control over the photoisomerization reaction can be obtained by a computational directed evolution approach on the ensembles of molecules with the pretwisted geometries.