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arxiv: 1310.6059 · v1 · pith:K7FB26W3new · submitted 2013-10-22 · ⚛️ physics.chem-ph · cond-mat.mtrl-sci· cond-mat.other· cond-mat.quant-gas

Many-body quantum chemistry for the electron gas: convergent perturbative theories

classification ⚛️ physics.chem-ph cond-mat.mtrl-scicond-mat.othercond-mat.quant-gas
keywords perturbativetheoriesclustercoupledelectronchemistryinteractionsquantum
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We investigate the accuracy of a number of wavefunction based methods at the heart of quantum chemistry for metallic systems. Using Hartree-Fock as a reference, perturbative (M{\o}ller-Plesset, MP) and coupled cluster (CC) theories are used to study the uniform electron gas model. Our findings suggest that non-perturbative coupled cluster theories are acceptable for modelling electronic interactions in metals whilst perturbative coupled cluster theories are not. Using screened interactions, we propose a simple modification to the widely-used coupled-cluster singles and doubles plus perturbative triples method (CCSD(T)) that lifts the divergent behaviour and is shown to give very accurate correlation energies for the homogeneous electron gas.

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