Do CCSD and approximate CCSD-F12 variants converge to the same basis set limits? The case of atomization energies

Abstract

While the title question is a clear 'yes' from purely theoretical arguments, the case is less clear for practical calculations with finite (one-particle) basis sets. To shed further light on this issue, the basis set limits of CCSD (coupled cluster theory with all single and double excitations) and of different approximate implementations of CCSD-F12 (explicitly correlated CCSD) have been investigated on detail for the W4-17 thermochemical benchmark. Near the CBS ([1-particle] complete basis set) limit, CCSD and CCSD(F12*) agree to within their respective uncertainties (about \pm0.04 kcal/mol) due to residual basis set incompleteness error, but a nontrivial difference remains between CCSD-F12b and CCSD(F12*), which is roughly proportional to the degree of static correlation. The observed basis set convergence behavior results from the superposition of a rapidly converging, attractive, CCSD[F12]--CCSD-F12b difference (consisting mostly of third-order terms), and a more slowly converging, repulsive, fourth-order difference between CCSD(F12*) and CCSD[F12]. For accurate thermochemistry, we recommend CCSD(F12*) over CCSD-F12b if at all possible. There are some indications that the nZaPa family of basis sets exhibits somewhat smoother convergence than the correlation consistent family.

(J. Chem. Phys., revised)

References in corpus (9)

• Towards standard methods for benchmark quality ab initio thermochemistry --- W1 and W2 theory
• W4 theory for computational thermochemistry: in pursuit of confident sub-kJ/mol predictions
• Quantum Entanglement in Fermionic Lattices
• Separation of Dynamic and Nondynamic Correlation
• Toward a W4-F12 approach: Can explicitly correlated and orbital-based ab initio CCSD(T) limits be reconciled?
• The cc-pV5Z-F12 basis set: reaching the basis set limit in explicitly correlated calculations
• Heats of formation of perchloric acid, HClO${}_4$, and perchloric anhydride, Cl${}_2$O${}_7$. Probing the limits of W1 and W2 theory
• A Simple 'Range Extender' for Basis Set Extrapolation Methods for MP2 and Coupled Cluster Correlation Energies
• Probing the basis set limit for thermochemical contributions of inner-shell correlation: Balance of core-core and core-valence contributions

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