Extending the definition of atomic basis sets to atoms with fractional nuclear charge

Abstract

Alchemical transformations showed that perturbation theory can be applied also to changes in the atomic nuclear charges of a molecule. The alchemical path that connects two different chemical species involves the conceptualization of a non-physical system in which atom possess a non-integer nuclear charge. A correct quantum mechanical treatment of these systems is limited by the fact that finite size atomic basis sets do not define exponents and contraction coefficients for fractional charge atoms. This paper is proposes a solution to this problem, and shows that a smooth interpolation of the atomic orbital coefficients and exponents across the periodic table is a convenient way to produce accurate alchemical predictions, even using small size basis sets.

References in corpus (24)

• SciPy 1.0--Fundamental Algorithms for Scientific Computing in Python
• Array Programming with NumPy
• Fast and Accurate Modeling of Molecular Atomization Energies with Machine Learning
• Recent developments in the PySCF program package
• Combining Machine Learning and Computational Chemistry for Predictive Insights Into Chemical Systems
• Machine learning prediction errors better than DFT accuracy
• Operators in Machine Learning: Response Properties in Chemical Space
• A review on non-relativistic fully numerical electronic structure calculations on atoms and diatomic molecules
• Machine Learning of Free Energies in Chemical Compound Space Using Ensemble Representations: Reaching Experimental Uncertainty for Solvation
• DQC: a Python program package for Differentiable Quantum Chemistry
• Fast and accurate predictions of covalent bonds in chemical space
• Structural and Electronic Properties of a Wide-gap Semiconductor Alloy: Zn_xMg_{1-x}S_ySe_{1-y}
• Fully numerical Hartree-Fock and density functional calculations. I. Atoms
• Exploring water adsorption on isoelectronically doped graphene using alchemical derivatives
• Polarized Gaussian basis sets from one-electron ions
• Rapid and accurate molecular deprotonation energies from quantum alchemy
• Atoms in molecules from alchemical perturbation density functional theory
• Al${}_x$Ga${}_{1-x}$As crystals with direct 2 eV band gaps from computational alchemy
• Effects of perturbation order and basis set on alchemical predictions
• Fast evaluation of solid harmonic Gaussian integrals for local resolution-of-the-identity methods and range-separated hybrid functionals
• Alchemical geometry relaxation
• Relative energies without electronic perturbations via Alchemical Integral Transform
• Alchemical diastereomers from antisymmetric alchemical perturbations
• The Alchemical Integral Transform revisited

Cited by in corpus (1)

• Antisymmetry rules of response properties in certain chemical spaces