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Bibliographic Details
Main Authors: Barman, Aditya, Jones, Gregory H., Martin, Jan M. L.
Format: Preprint
Published: 2026
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Online Access:https://arxiv.org/abs/2605.19860
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Table of Contents:
  • We extend the CCSDTQ implementation in CFOUR to UHF and ROHF references and demonstrate its efficiency. We apply it to basis set convergence of post-CCSDT(Q) corrections for the W4-08 thermochemical dataset. Convergence of (Q)$_Λ$--(Q) is relatively rapid. For difficult species (e.g., B2, O3), CCSDTQ--CCSDT(Q)$_Λ$ may converge more slowly than (5)$_Λ$, but the effects and and basis-set trends oppose each other. Consequently, a single-shot CCCSDTQ(5)$_Λ$-CCSDT(Q)$_Λ$ correction appears most efficient. For radicals with bifurcating UHF solutions, energetics of the `less spin-contaminated' solution are clearly more well-behaved. Our best computed adiabatic electron affinity of ozone is in excellent agreement with experiment.