4.7 Article

Communication: Random-phase approximation excitation energies from approximate equation-of-motion coupled-cluster doubles

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JOURNAL OF CHEMICAL PHYSICS
卷 149, 期 4, 页码 -

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AMER INST PHYSICS
DOI: 10.1063/1.5032314

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  1. University of Chicago
  2. Air Force Office of Scientific Research [FA9550-18-1-0058]

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The ground-state correlation energy calculated in the random-phase approximation (RPA) is known to be identical to that calculated using a subset of terms appearing in coupled-cluster theory with double excitations (CCD). In particular, for particle-hole (ph) RPA this equivalence requires keeping only those terms that generate time-independent ring diagrams, and for particle-particle (pp) RPA it requires keeping only those terms that generate ladder diagrams. Here I show that these identities extend to excitation energies, for which those calculated in each RPA are identical to those calculated using approximations to equation-of-motion coupled-cluster theory with double excitations (EOM-CCD). The equivalence requires three approximations to EOM-CCD: first, the ground-state CCD amplitudes are obtained from the ring-CCD or ladder-CCD equations (the same as for the correlation energy); second, the EOM eigenvalue problem is truncated to the minimal subspace, which is one particle + one hole for ph-RPA and two particles or two holes for pp-RPA; third, the similarity transformation of the Fock operator must be neglected, as it corresponds to a Brueckner-like dressing of the single-particle propagator, which is not present in the conventional RPA. Published by AIP Publishing.

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