Nanosecond Photodynamics Simulations of a Cis-Trans Isomerization Are Enabled by Machine Learning

Photochemical reactions are being increasingly used to construct complex molecular architectures with mild and straightforward reaction conditions. Computational techniques are increasingly important to understand the reactivities and chemoselectivities of photochemical isomerization reactions because they offer molecular bonding information along the excited-state(s) of photodynamics. These photodynamics simulations are resource-intensive and are typically limited to 1–10 picoseconds and 1,000 trajectories due to high computational cost. Most organic photochemical reactions have excited-state lifetimes exceeding 1 picosecond, which places them outside possible computational studies. Westermeyr et al. demonstrated that a machine learning approach could significantly lengthen photodynamics simulation times for a model system, methylenimmonium cation (CH₂NH₂⁺).

We have developed a Python-based code, Python Rapid Artificial Intelligence Ab Initio Molecular Dynamics (PyRAI²MD), to accomplish the unprecedented 10 ns cis-trans photodynamics of trans-hexafluoro-2-butene (CF₃–CH=CH–CF₃) in 3.5 days. The same simulation would take approximately 58 years with ground-truth multiconfigurational dynamics. We proposed an innovative scheme combining Wigner sampling, geometrical interpolations, and short-time quantum chemical trajectories to effectively sample the initial data, facilitating the adaptive sampling to generate an informative and data-efficient training set with 6,232 data points. Our neural networks achieved chemical accuracy (mean absolute error of 0.032 eV). Our 4,814 trajectories reproduced the S₁ half-life (60.5 fs), the photochemical product ratio (trans: cis = 2.3: 1), and autonomously discovered a pathway towards a carbene. The neural networks have also shown the capability of generalizing the full potential energy surface with chemically incomplete data (trans → cis but not cis → trans pathways) that may offer future automated photochemical reaction discoveries.