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Relativistic Segmented Correlation Consistent Basis Sets for the 5p and 6p Elements.

George Schoendorff¹, Jerry A Boatz¹

¹Propellants Branch, Rocket Propulsion Division, Aerospace Systems Directorate, Air Force Research Laboratory, AFRL/RQRP, Edwards Air Force Base, Edwards, California 93524, United States.

The Journal of Physical Chemistry. A

|July 19, 2022

Summary

This summary is machine-generated.

New relativistic basis sets for 5p and 6p elements offer accurate computational chemistry results. These segmented basis sets provide significant speedups without compromising accuracy in ionization potentials, electron affinities, and bond properties.

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Area of Science:

Computational chemistry
Quantum chemistry
Relativistic quantum chemistry

Background:

Correlation-consistent basis sets are crucial for accurate quantum chemical calculations.
Relativistic effects are important for heavy elements (5p and 6p).
Segmented basis sets can offer computational advantages over generally contracted ones.

Purpose of the Study:

Reoptimize relativistic all-electron triple-ζ (TZ) and quadruple-ζ (QZ) basis sets using a segmented contraction scheme.
Evaluate the accuracy and efficiency of these new segmented basis sets compared to generally contracted ones.
Assess the performance for various molecular properties including ionization potentials, electron affinities, bond lengths, vibrational frequencies, and bond dissociation energies.

Main Methods:

Optimization of relativistic all-electron basis sets (TZ and QZ) with a segmented contraction scheme.
Coupled-cluster calculations employing single, double, and perturbative triple excitations (CC(2,3)).
Comparison of computed properties using segmented versus generally contracted basis sets.

Main Results:

Computed properties using segmented basis sets closely match those from generally contracted analogues.
Deviations in ionization potentials and electron affinities are within 1 kcal mol^-1.
Relative deviations in bond lengths are within 0.02 Å, and harmonic frequencies differ by less than 3%.
Mean absolute deviations in bond dissociation energies are low, especially when outer-core electrons are correlated (0.14 and 0.10 kcal mol^-1 for TZ and QZ).
Segmented basis sets provide significant speedups (32.8x to 82.9x) in Fock matrix formation.

Conclusions:

Reoptimized segmented relativistic basis sets provide high accuracy comparable to generally contracted versions.
These new basis sets offer substantial computational efficiency gains for 5p and 6p elements.
The segmented basis sets retain the systematic convergence properties of the correlation-consistent family.