How `Nonvariational' Are Approximate Coupled Cluster Methods In Practice?

Abstract

While limited coupled cluster theory is \textit{formally} nonvariational, it is not broadly appreciated whether this is a major issue \textit{in practice}. We carried out a detailed comparison with \textit{de facto} full CI energies for a relatively large and diverse set of molecules. Fully iterative limited CC methods such as CCSDT, CCSDTQ, CCSDTQ5 do represent practical upper bounds to the FCI energy. While quasiperturbative approaches such as CCSD(T) and especially CCSDT(Q) may significantly over-correlate molecules if there is significant static correlation, this is much less of an issue with Lambda approaches such as CCSDT(Q)$\Lambda$.