Eike S. Eberhard

Eike S. Eberhard, Luca A. Thiede, Abdul Aldossary et al.

Machine-learned (ML) exchange-correlation (XC) functionals aim to replace human-designed density functional approximations by learning directly from reference data, but they still do not consistently outperform traditional $\mathcal{O}(N^4)$-scaling hybrid functionals. We study a hybrid-distillation setting in which $\mathcal{O}(N^3)$-scaling ML-XC functionals are trained to reproduce B3LYP/def2-SVP targets. We introduce Derivative Informed XC-Loss (DI-Loss), a loss that incorporates additional information from the reference hybrid functional by supervising first and second derivatives of the energy on the Grassmannian of admissible density matrices. Rather than only matching the self-consistent fixed point, DI-Loss aligns the local first- and second-order response of the learned functional with that of the target functional. Across four evaluated architectures, DI-Loss consistently improves the main energy metrics. Averaged uniformly across architectures, the total-energy MAE decreases by 66% relative to energy and density supervision alone. The density-sensitive mean-field energy metric $E_ρ$ improves from $1.2$ to $0.8$ mEh on average, while dipole and $\mathcal{L}_2$ density errors do not improve uniformly. We further show that densities from the distilled functionals reduce hybrid-functional SCF iterations by up to 50%. In downstream TDDFT calculations, Hessian supervision improves excited-state predictions, with XCdiff reducing the mean excitation-energy MAE by 19 - 35%.

Eike S. Eberhard, Viktor Kotsev, Timm Güthle et al.

Machine learning methods that predict initial guesses from molecular geometry can reduce this cost, but matrix-prediction models fail when extrapolating to larger molecules, degrading rather than accelerating convergence [Liu et al. 2025]. We show that this failure is a supervision problem, not an extrapolation problem: models trained on ground-state targets fit those targets well out of distribution, yet produce initial guesses that slow convergence. Solver-Aligned Initialization Learning (SAIL) resolves this for both Hamiltonian and density matrix models by differentiating through the SCF solver end-to-end. We introduce the Effective Relative Iteration Count (ERIC), a correction to the commonly used RIC that accounts for hidden Fock-build overhead. On QM40, containing molecules up to 4$\times$ larger than the training distribution, SAIL reduces ERIC by 37% (PBE), 33% (SCAN), and 27% (B3LYP), more than doubling the previous state-of-the-art reduction on B3LYP (10%). On QMugs molecules 10$\times$ the training size, SAIL delivers a 1.25$\times$ wall-time speedup at the hybrid level of theory, extending ML SCF acceleration to large drug-like molecules.