Asymptotics-based CI models for atoms: properties, exact solution of a minimal model for Li to Ne, and application to atomic spectra

Physics – Mathematical Physics

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26 pages, 3 figures, submitted to SIAM Multiscale Model. Sim

Scientific paper

Configuration-Interaction (CI) models are approximations to the electronic Schr\"odinger equation which are widely used for numerical electronic structure calculations in quantum chemistry. Based on our recent closed-form asymptotic results for the full atomic Schr\"odinger equation in the limit of fixed electron number and large nuclear charge, we introduce a class of CI models for atoms which reproduce, at fixed finite model dimension, the correct Schr\"odinger eigenvalues and eigenstates in this limit. We solve exactly the ensuing minimal model for the second period atoms, Li to Ne. The energy levels and eigenstates are in remarkably good agreement with experimental data (comparable to that of much larger scale numerical simulations in the literature), and facilitate a mathematical understanding of various spectral, chemical and physical properties of small atoms.

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