A new open-shell CCSDTQ implementation and its application to the basis set convergence of post-CCSDT(Q) corrections in computational thermochemistry

Abstract

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)$_\Lambda$--(Q) is relatively rapid. For difficult species (e.g., B2, O3), CCSDTQ--CCSDT(Q)$_\Lambda$ may converge more slowly than (5)$_\Lambda$, but the effects and and basis-set trends oppose each other. Consequently, a single-shot CCCSDTQ(5)$_\Lambda$-CCSDT(Q)$_\Lambda$ correction appears most efficient. For radicals with bifurcating UHF solutions, energetics of the `less spin-contaminated' solution are clearly more well-behaved. Alternatives to a single-shot CCSDTQ(5)$_\Lambda$--CCSDT(Q)$_\Lambda$ correction are evaluating (5)$_\Lambda$ either in a truncated cc-pVDZ(p,s) basis set, or by means of frozen natural orbitals. Our best computed adiabatic electron affinity of ozone is in excellent agreement with experiment.