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Bibliographic Details
Main Authors: Briling, Ksenia R., Alonso, Yannick Calvino, Fabrizio, Alberto, Corminboeuf, Clemence
Format: Preprint
Published: 2023
Subjects:
Online Access:https://arxiv.org/abs/2309.02950
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Table of Contents:
  • Recently, we introduced a class of molecular representations for kernel-based regression methods -- the spectrum of approximated Hamiltonian matrices (SPA$^\mathrm{H}$M) -- that takes advantage of lightweight one-electron Hamiltonians traditionally used as an SCF initial guess. The original SPA$^\mathrm{H}$M variant is built from occupied-orbital energies (ie, eigenvalues) and naturally contains all the information about nuclear charges, atomic positions, and symmetry requirements. Its advantages were demonstrated on datasets featuring a wide variation of charge and spin, for which traditional structure-based representations commonly fail. SPA$^\mathrm{H}$M(a,b), as introduced here, expand the eigenvalue SPA$^\mathrm{H}$M into local and transferable representations. They rely upon one-electron density matrices to build fingerprints from atomic and bond density overlap contributions inspired from preceding state-of-the-art representations. The performance and efficiency of SPA$^\mathrm{H}$M(a,b) is assessed on the predictions for datasets of prototypical organic molecules (QM7) of different charges and azoheteroarene dyes in an excited state. Overall, both SPA$^\mathrm{H}$M(a) and SPA$^\mathrm{H}$M(b) outperform state-of-the-art representations on difficult prediction tasks such as the atomic properties of charged open-shell species and of $π$-conjugated systems.