Correlation Energy Expressions from the Adiabatic-Connection Fluctuation–Dissipation Theorem Approach

Ángyán, János G.; Liu, Ru-Fen; Toulouse, Julien; Jansen, Georg

doi:10.1021/ct200501r

Cited by 133 publications

(84 citation statements)

References 73 publications

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“…For comparison purposes, we also provide results obtained from the rCCD-based SOSEX approximation [11,44] and the dRPA-II approximation as derived within the adiabatic connection approach [34]. As already discussed in Sec.…”

Section: Numerical Resultsmentioning

confidence: 99%

“…34. It is important to mention that in this context the MP2 correlation energy represents the first non-vanishing contribution to a converging series only if all the eigenvalues of Π 0 (iω)K are smaller than 1.…”

Section: B Rpa+sosexmentioning

confidence: 99%

“…Additionally, RPAx-Ia is more stable than RPAx-I (Eq. 25) when using PBE as starting point [34]. It is important to notice that the PBE and the non-self-consistent PBE0 (post-PBE) approximations lead to the significant MAEs of 4.68 and 4.57 kcal/mol, respectively.…”

Section: Application To Reaction Energiesmentioning

confidence: 99%

“…Additionally, according to the classification and nomenclature proposed in Ref. 34, RPA methods for the ground-state correlation energy can be sought in two main flavors: either by the complete neglect of the exchange integrals, i.e. by taking the contrac-tion of the dRPA response function with non-antisymmetrized two-electron integrals (dRPA-I), or by a full consideration of non-local exchange, when antisymmetrized two-electron integrals are contracted with the RPAx response function matrix elements (RPAx-II).…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Dielectric Matrix Formulation of Correlation Energies in the Random Phase Approximation: Inclusion of Exchange Effects

Mussard¹,

Rocca²,

Jansen

et al. 2016

J. Chem. Theory Comput.

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Starting from the general expression for the ground state correlation energy in the adiabatic connection fluctuation dissipation theorem (ACFDT) framework, it is shown that the dielectric matrix formulation, which is usually applied to calculate the direct random phase approximation (dRPA) correlation energy, can be used for alternative RPA expressions including exchange effects. Within this famework, the ACFDT analog of the second order screened exchange (SOSEX) approximation leads to a logarithmic formula for the correlation energy similar to the direct RPA expression. Alternatively, the contribution of the exchange can be included in the kernel used to evaluate the response functions. In this case the use of an approximate kernel is crucial to simplify the formalism and to obtain a correlation energy in logarithmic form. Technical details of the implementation of these methods are discussed and it is shown that one can take advantage of density fitting or Cholesky decomposition techniques to improve the computational efficiency; a discussion on the numerical quadrature made on the frequency variable is also provided. A series of test calculations on atomic correlation energies and molecular reaction energies shows that exchange effects are instrumental to improve over direct RPA results.

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Section: Numerical Resultsmentioning

confidence: 99%

Section: B Rpa+sosexmentioning

confidence: 99%

Section: Application To Reaction Energiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Dielectric Matrix Formulation of Correlation Energies in the Random Phase Approximation: Inclusion of Exchange Effects

Mussard¹,

Rocca²,

Jansen

et al. 2016

J. Chem. Theory Comput.

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“…An intermediate abinitio correlation method, the random-phase approximation, which sums certain perturbation diagrams to infinite order, has also been adapted to the range-separated scheme [16][17][18][19][20] and has lead to good results.…”

Section: Introductionmentioning

confidence: 99%

Short range DFT combined with long-range local RPA within a range-separated hybrid DFT framework

Chermak¹,

Mussard²,

Ángyán³

et al. 2012

Chemical Physics Letters

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Selecting excitations in localized orbitals to calculate long-range correlation contributions to rangeseparated density-functional theory can reduce the overall computational effort significantly. Beyond simple selection schemes of excited determinants, the dispersion-only approximation, which avoids counterpoise-corrected monomer calculations, is shown to be particularly interesting in this context, which we apply to the random-phase approximation. The approach has been tested on dimers of formamide, water, methane and benzene.

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PtO_xCl_y(OH)_z(H₂O)_n Complexes under Oxidative and Reductive Conditions: Impact of the Level of Theory on Thermodynamic Stabilities

2022

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Platinum-based catalysts with Cl À , OH À , O 2À and H 2 O ligands, are involved in many industrial processes. Their final chemical properties are impacted by calcination and reduction applied during the preparation and activation steps. We investigate their stability under these reactive conditions with density functional theory (DFT). We benchmark various functionals (PBE-dDsC, optPBE, B3LYP, HSE06, PBE0, TPSS, RTPSS and SCAN) against ACFDT-RPA. PBE-dDsC is well adapted, although hybrid functionals are more accurate for redox reactions. Thermody-namic phase diagrams are determined by computing the chemical potential of the species as a function of temperature and partial pressures of H 2 O, HCl, O 2 and H 2 . The stability and nature of the Pt species are highly sensitive to the activation conditions. Under O 2 , high temperatures favour PtO 2 while under H 2 , platinum is easily reduced to Pt(0). Chlorine modifies the coordination sphere of platinum during calcination by stabilizing PtCl 4 and shifts the reduction of platinum to higher temperatures under H 2 .

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Correlation Energy Expressions from the Adiabatic-Connection Fluctuation–Dissipation Theorem Approach

Cited by 133 publications

References 73 publications

Dielectric Matrix Formulation of Correlation Energies in the Random Phase Approximation: Inclusion of Exchange Effects

Dielectric Matrix Formulation of Correlation Energies in the Random Phase Approximation: Inclusion of Exchange Effects

Short range DFT combined with long-range local RPA within a range-separated hybrid DFT framework

PtO_xCl_y(OH)_z(H₂O)_n Complexes under Oxidative and Reductive Conditions: Impact of the Level of Theory on Thermodynamic Stabilities

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Correlation Energy Expressions from the Adiabatic-Connection Fluctuation–Dissipation Theorem Approach

Cited by 133 publications

References 73 publications

Dielectric Matrix Formulation of Correlation Energies in the Random Phase Approximation: Inclusion of Exchange Effects

Dielectric Matrix Formulation of Correlation Energies in the Random Phase Approximation: Inclusion of Exchange Effects

Short range DFT combined with long-range local RPA within a range-separated hybrid DFT framework

PtOxCly(OH)z(H2O)n Complexes under Oxidative and Reductive Conditions: Impact of the Level of Theory on Thermodynamic Stabilities

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PtO_xCl_y(OH)_z(H₂O)_n Complexes under Oxidative and Reductive Conditions: Impact of the Level of Theory on Thermodynamic Stabilities