Applications of the <scp>MBPT</scp> in the localized representation

Kapuy, E.; Bartha, F.; Bogár, Ferenc; Csépes, Zoltán; Kozmutza, C.

doi:10.1002/qua.560380209

Cited by 46 publications

(20 citation statements)

References 40 publications

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“…24), the contributions of the higher-order localization corrections are much less than are the neglected third-order canonical corrections, their inclusion would be easy but unnecessary [29]. We use atomic units throughout this paper.…”

Section: Results Obtained For the Contributions Of The Localized Orbimentioning

confidence: 98%

Localized orbitals for the description of molecular interaction

Kozmutza

Kapuy

1990

Int J of Quantum Chemistry

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The intermolecular interaction between the molecules CH20 and NH, was investigated by the supermolecule method. The interaction energies were first calculated at the ab initio SCF level, and the electron correlation was included via second-order M0ller-Plesset perturbation theory (MP~). The basis set superposition error (BSSE) was taken into account by the counter-poise (m) method. The occupied and the virtual canonical molecular orbitals (CMOS) of the supermolecule were separately localized by the Boys' procedure. The correlation correction was calculated by the many-body perturbation theory (MBFT) in the localized representation. Contributions of the third-and fourth-order localized diagrams were added to those of the second-order canonical diagram. This procedure gives a correction nearly equivalent to that of M P~. The possibility to separate LMO contributions responsible for the dispersion interaction was investigated.

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Section: Results Obtained For the Contributions Of The Localized Orbimentioning

confidence: 98%

Localized orbitals for the description of molecular interaction

Kozmutza

Kapuy

1990

Int J of Quantum Chemistry

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“…The first is based on the Kapuy MP2 (KMP2) approximation, [31][32][33] which neglects non-diagonal elements of the occupied block of the Fock matrix (or rather, excludes them from the definition of the zerothorder operator) to give…”

Section: Orbital Optimization In Osv-mp2mentioning

confidence: 99%

Optimization of orbital-specific virtuals in local Møller-Plesset perturbation theory

Kurashige

Yang

Chan

et al. 2012

The Journal of Chemical Physics

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We present an orbital-optimized version of our orbital-specific-virtuals second-order Møller-Plesset perturbation theory (OSV-MP2). The OSV model is a local correlation ansatz with a small basis of virtual functions for each occupied orbital. It is related to the Pulay-Saebø approach, in which domains of virtual orbitals are drawn from a single set of projected atomic orbitals; but here the virtual functions associated with a particular occupied orbital are specifically tailored to the correlation effects in which that orbital participates. In this study, the shapes of the OSVs are optimized simultaneously with the OSV-MP2 amplitudes by minimizing the Hylleraas functional or approximations to it. It is found that optimized OSVs are considerably more accurate than the OSVs obtained through singular value decomposition of diagonal blocks of MP2 amplitudes, as used in our earlier work. Orbital-optimized OSV-MP2 recovers smooth potential energy surfaces regardless of the number of virtuals. Full optimization is still computationally demanding, but orbital optimization in a diagonal or Kapuy-type MP2 approximation provides an attractive scheme for determining accurate OSVs.

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“…As stated in the introduction, past work on Kapuy's MPBPT theory in local orbitals have always required the addition of third and higher order perturbative corrections in order to account for the off-diagonal elements of the Fock matrix. In other words, Kapuy et al [12,13,14,18] have focused on computing the quantity…”

Section: Kmp2 Energies Of Localized Orbitalsmentioning

confidence: 99%

“…[12,13,14,15,16,17,18] In particular, Kapuy's approach was to consider the Fock operator in a basis of localized orthonormal occupied and virtual orbitals, and then set the primary Hamiltonian as the diagonal piece of the Fock operator in this basis. Kapuy then treated the off-diagonal elements of the Fock-matrix and the two-electron coulomb term together as the joint perturbation in MBPT.…”

Section: Introductionmentioning

confidence: 99%

A localized basis that allows fast and accurate second-order Møller-Plesset calculations

Subotnik

Head‐Gordon

2005

The Journal of Chemical Physics

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We present a method for computing a basis of localized orthonormal orbitals (both occupied and virtual), in whose representation the Fock matrix is extremely diagonal-dominant. The existence of these orbitals is shown empirically to be sufficient for achieving highly accurate MP2 energies, calculated according to Kapuy's method. This method (which we abbreviate KMP2), which involves a different partitioning of the n-electron Hamiltonian, scales at most quadratically with potential for linearity in the number of electrons. As such, we believe the KMP2 algorithm presented here could be the basis of a viable approach to local correlation calculations.

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Applications of the MBPT in the localized representation

Cited by 46 publications

References 40 publications

Localized orbitals for the description of molecular interaction

Localized orbitals for the description of molecular interaction

Optimization of orbital-specific virtuals in local Møller-Plesset perturbation theory

A localized basis that allows fast and accurate second-order Møller-Plesset calculations

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