Temperature dependence of the cooperative out-of-equilibrium elastic switching in a spin-crossover material
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Roman Bertoni, Eric Collet, Hervé Cailleau, Marie-Laure Boillot, Antoine Tissot, Jérôme Laisney, Cristian Enachescu, Maciej Lorenc
We present a study of a molecular material, [FeIII(3-MeO-SalEen)2]PF6, undergoing cooperative reversible photo-induced transition between low-spin state and high-spin state. By using temporally multiscale pump–probe laser spectroscopy, we explore the key parameters that influence the low-spin to high-spin conversion efficiency through long range elastic intermolecular interactions during the so-called elastic step, where crystalline volume expansion takes place. We rationalize our findings using Monte Carlo simulations, and a mechano-elastic model. The experimental results and the simulations support the existence of a fast mechanism by which molecules cooperatively switch through coupling to the lattice strain. The efficiency of the coupling process is shown to depend on several parameters including the initial thermal population and the instantaneous photo-induced population among others. Far below the crossover temperature, the elastic self-amplification occurs above a threshold photo-excitation. On approaching the thermal crossover, the threshold disappears and the photo-elastic conversion increases.
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.














