On the Performance of QTP Functionals Applied to Second-Order Response Properties II: Dynamic Polarizability and Long-Range C 6 Coefficients

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Abstract
This work is the second in the series "On the performance of QTP functionals applied to second-order response properties." In the first paper (J. Chem. Phys. 2025, 162, 054105), we demonstrated the good performance of Quantum Theory Project functionals in predicting static perturbed second-order properties, such as static polarizabilities, nuclear magnetic resonance (NMR) spin-spin coupling constants, and NMR chemical shifts. In the present study, we focus on frequency-dependent properties, namely dynamic polarizabilities and C6 dispersion coefficients. For completeness, a total of 25 exchange-correlation (XC) functionals were investigated. Dynamic polarizabilities were evaluated at five different perturbation wavelengths: 632.99, 594.10, 543.52, 514.50, and 325.13 nm. This property was also computed using HF, LR-CC3, and EOM-CCSD. In general, EOM-CCSD results are very close to those obtained with linear-response CC3, except at the highest frequency. Among Kohn-Sham calculations, TPSS0 and QTP01 showed the best overall performance for dynamic polarizabilities. We also assessed how well QTP functionals reproduce the pole structure of the CO molecule. For the C6 dispersion coefficients, calculations were performed using the Casimir-Polder equation. The best overall performance was obtained with O3LYP; however, the first 11 ranked functionals show very similar accuracy. Within the QTP family, QTP01 and LC-QTP provide the best results for C6 coefficients.
Funding Information
  • Division of Chemistry (2430408)
  • Air Force Office of Scientific Research (FA9550-23-1-0118)

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