Dual Breaking of Molecular Orbitals and Spatial Symmetry in an Optically Controlled Ferroelectric

As particles carry quantified energy, photon radiation enables orbital transitions of energy levels, leading to changes in the spin state of electrons. The resulting switchable structural bistability may bring a new paradigm for manipulating ferroelectric polarization. However, the studies on molecular orbital breaking in the ferroelectric field remain blank. Here, for the first time, a new mechanism of ferroelectrics—dual breaking of molecular orbitals and spatial symmetry, demonstrated in a photochromic organic crystal with light‐induced polarization switching, is formally proposed. By alternating the ultraviolet/visible light irradiation, the states of electron spin and the radial distribution p atomic orbitals experience a change, showing a reversible switch from “shoulder‐to‐shoulder” form to a “head‐to‐head” form. This reflects a reversible conversion between π and σ bonds, which induces and couples with the variation of spatial symmetry. The intersection of spatial symmetry breaking and molecular orbital breaking in ferroelectrics present in this work will be more conducive to data encryption and anticounterfeiting. Dual breaking of molecular orbitals and spatial symmetry enables the optical control of two ferroelectric states between the closed‐ring and open‐ring forms of a photochromic organic ferroelectric, which is an unprecedented mechanism in ferroelectrics and brings a new paradigm for manipulating ferroelectric polarization.