Alchemical geometry relaxation

Abstract

We propose to relax geometries throughout chemical compound space (CCS) using alchemical perturbation density functional theory (APDFT). APDFT refers to perturbation theory involving changes in nuclear charges within approximate solutions to Schrödinger's equation. We give an analytical formula to calculate the mixed second order energy derivatives with respect to both, nuclear charges and nuclear positions (named "alchemical force"), within the restricted Hartree-Fock case. We have implemented and studied the formula for its use in geometry relaxation of various reference and target molecules. We have also analysed the convergence of the alchemical force perturbation series, as well as basis set effects. Interpolating alchemically predicted energies, forces, and Hessian to a Morse potential yields more accurate geometries and equilibrium energies than when performing a standard Newton Raphson step. Our numerical predictions for small molecules including BF, CO, N2, CH${}_4$, NH${}_3$, H${}_2$O, and HF yield mean absolute errors of of equilibrium energies and bond lengths smaller than 10 mHa and 0.01 Bohr for 4${}^{\text{th}}$ order APDFT predictions, respectively. Our alchemical geometry relaxation still preserves the combinatorial efficiency of APDFT: Based on a single coupled perturbed Hartree Fock derivative for benzene we provide numerical predictions of equilibrium energies and relaxed structures of all the 17 iso-electronic charge-netural BN-doped mutants with averaged absolute deviations of $\sim$27 mHa and $\sim$0.12 Bohr, respectively.

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Cited by in corpus (4)

• Relative energies without electronic perturbations via Alchemical Integral Transform
• Molecular Hessian matrices from a machine learning random forest regression algorithm
• Extending the definition of atomic basis sets to atoms with fractional nuclear charge
• Antisymmetry rules of response properties in certain chemical spaces