Genarris 3.0: Generating Close-Packed Molecular Crystal Structures with Rigid Press.

Polymorphism in molecular crystals influences their properties and performance. Crystal structure prediction (CSP) can help explore the crystal structure landscape and discover potentially stable polymorphs computationally. We present a new version of the Genarris open-source code, which generates random molecular crystal structures in all space groups and applies physical constraints on intermolecular distances. The main new feature in Genarris 3.0 is the "Rigid Press" algorithm, which uses a regularized hard-sphere potential to compress the unit cell and achieve a maximally close-packed structure based on purely geometric considerations without performing any energy evaluations. In addition, Genarris 3.0 is interfaced with machine-learned interatomic potentials (MLIPs) to accelerate the exploration of the potential energy landscape. We present a new clustering and down-selection workflow that employs the MACE-OFF23(L) MLIPs to perform geometry optimization and energy ranking in the early stages. We use Genarris 3.0 to successfully predict the structure of six targets: aspirin, Target I and Target XXII from previous CSP blind tests, and the energetic materials HMX, CL-20, and DNI. We further analyze the performance of MACE-OFF23(L) compared to dispersion-inclusive density functional theory (DFT) for geometry relaxation and energy ranking. We find significant variability in the performance of MACE-OFF23(L) across chemically diverse targets with particularly poor performance for energetic materials, which is mitigated by our clustering and down-selection procedure. Genarris 3.0 can thus be used effectively to perform CSP and to generate molecular crystal data sets for training ML models.