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DOE OSTI · 2478735

Removing Basis Set Incompleteness Error in Finite-Temperature Electronic Structure Calculations: Two-Electron Systems

Van Benschoten, William Z.·Shepherd, James J.
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Abstract

We investigate the basis-set-size dependence for quantities related to interacting electrons in the canonical ensemble. Calculations are performed using exact diagonalization (finite temperature full configuration interaction method) on two-electron model systems–the uniform electron gas (UEG) and the helium atom. Our data reproduce previous observations of a competition for how the internal energy converges between the ground-state correlation energy and the high-temperature kinetic energy. We explore how this can be related to component parts of the internal energy including kinetic, exchange, and correlation energies and show there is surprising nuance in how this can be broken down into mostly monotonically converging quantities. We also show that separation of the free energy into a free energy with/without correlation allows for monotonic convergence with basis set size due to the variational principle. We find that the free energy convergence matches the previously observed convergence properties of the internal energy. We discuss the free energy divergence that happens when converging a finite basis analytical hydrogen atom to the complete basis set limit and compare this to the energies of a helium atom in a large periodic box. Reducing the box size, we saw convergence trends for the helium atom that were similar to the UEG.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRYBasis setsEnergyFree energyInternal energyQuantum mechanics

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Van Benschoten, William Z., Shepherd, James J.. 2024-11-25. Removing Basis Set Incompleteness Error in Finite-Temperature Electronic Structure Calculations: Two-Electron Systems. https://doi.org/10.1021/acs.jpca.4c03769

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