Arbitrarily accurate quantum alchemy

doi:10.1063/5.0073941

2021-12-08

Guido Falk von Rudorff *

DOI：10.1063/5.0073941

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摘要

En 中文

Doping compounds can be considered a perturbation to the nuclear charges in a molecular Hamiltonian. Expansions of this perturbation in a Taylor series, i.e., quantum alchemy, have been used in the literature to assess millions of derivative compounds at once rather than enumerating them in costly quantum chemistry calculations. So far, it was unclear whether this series even converges for small molecules, whether it can be used for geometry relaxation, and how strong this perturbation may be to still obtain convergent numbers. This work provides numerical evidence that this expansion converges and recovers the self-consistent energy of Hartree-Fock calculations. The convergence radius of this expansion is quantified for dimer examples and systematically evaluated for different basis sets, allowing for estimates of the chemical space that can be covered by perturbing one reference calculation alone. Besides electronic energy, convergence is shown for density matrix elements, molecular orbital energies, and density profiles, even for large changes in electronic structure, e.g., transforming He-3 into H-6. Subsequently, mixed alchemical and spatial derivatives are used to relax H-2 from the electronic structure of He alone, highlighting a path to spatially relaxed quantum alchemy. Finally, the underlying code that allows for arbitrarily accurate evaluation of restricted Hartree-Fock energies and arbitrary order derivatives is made available to support future method development.

Keyword:

MOLECULAR-ORBITAL METHODS

GAUSSIAN-BASIS SETS

DENSITY-FUNCTIONAL THEORY

NONNUCLEAR ATTRACTORS

LINEAR-RESPONSE

ATOMS LI

CHEMISTRY

DERIVATIVES

PRINCIPLES

CONSTANTS