Origin of inverse volume scaling in periodic coupled cluster calculations towards thermodynamic limit
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Coupled cluster theory is considered to be the “gold standard” ansatz of molecular quantum chemistry. The finite-size error of the correlation energy in periodic coupled cluster calculations for three-dimensional insulating systems has been observed to satisfy the inverse volume scaling, even in the absence of any correction schemes. This is surprising, as simpler theories that utilize only a subset of the coupled cluster diagrams exhibit much slower decay of the finite-size error, which scales inversely with the length of the system. In this study, we present a rigorous numerical analysis that explains the underlying mechanisms behind this phenomenon in the context of coupled cluster doubles (CCD) calculations, and reconciles a few seemingly paradoxical statements with respect to the finite-size scaling. Our findings also have implications on how to effectively address finite-size errors in practical quantum chemistry calculations for periodic systems.
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