Post-CCSD(T) corrections to bond distances and vibrational frequencies: the power of Λ

Abstract

The importance of post-CCSD(T) corrections as high as CCSDTQ56 for ground-state spectroscopic constants ( D e , ω e , ω e x e , and α e ) has been surveyed for a sample of two dozen mostly heavy-atom diatomics spanning a broad range of static correlation strength. While CCSD(T) is known to be an unusually felicitous ‘Pauling point’ between accuracy and computational cost, performance leaves something to be desired for molecules with strong static correlation. We find CCSDT(Q) Λ to be the next ‘sweet spot’ up, of comparable or superior quality to the much more expensive CCSDTQ. A similar comparison applies to CCSDTQ(5) Λ vs. CCSDTQ5, while CCSDTQ5(6) Λ is essentially indistinguishable from CCSDTQ56. A composite of CCSD(T)-X2C/ACV5Z-X2C with [CCSDT(Q) Λ – CCSD(T)]/cc-pVTZ or even cc-pVDZ basis sets appears highly effective for computational vibrational spectroscopy. Unlike CCSDT(Q) which breaks down for the ozone vibrational frequencies, CCSDT(Q) Λ handles them gracefully.