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Poul Jørgensen

Molecular gradient for second-order Møller-Plesset perturbation theory using the divide-expand-consolidate (DEC) scheme

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We demonstrate that the divide-expand-consolidate (DEC) scheme – which has previously been used to determine the second-order Møller–Plesset (MP2) correlation energy – can be applied to evaluate the MP2 molecular gradient in a linear-scaling and embarrassingly parallel manner using a set of local Hartree–Fock orbitals. All manipulations of four-index quantities (describing electron correlation effects) are carried out using small local orbital fragment spaces, whereas two-index quantities are treated for the full molecular system. The sizes of the orbital fragment spaces are determined in a black-box manner to ensure that the error in the DEC-MP2 correlation energy compared to a standard MP2 calculation is proportional to a single input threshold denoted the fragment optimization threshold (FOT). The FOT also implicitly controls the error in the DEC-MP2 molecular gradient as substantiated by a theoretical analysis and numerical results. The development of the DEC-MP2 molecular gradient is the initial step towards calculating higher order energy derivatives for large molecular systems using the DEC framework, both at the MP2 level of theory and for more accurate coupled-cluster methods.
TidsskriftJournal of Chemical Physics
Antal sider20
StatusUdgivet - 2012

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