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

Mussard, Bastien; Rocca, Dario; Jansen, Georg; Ángyán, János G.

doi:10.1021/acs.jctc.5b01129

Cited by 32 publications

(35 citation statements)

References 60 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The exact xc-energy [second term on the rhs of Eq (7)] can be further separated into the KS exact-exchange (EXX) energy 32) and the ACFDT correlation energy determined by the difference between the interacting and non-interacting KS response functions…”

Section: Technical Aspectsmentioning

confidence: 99%

Beyond the random phase approximation with a local exchange vertex

2018

View full text Add to dashboard Cite

With the aim of constructing an electronic structure approach that systematically goes beyond the GW and random phase approximation (RPA) we introduce a vertex correction based on the exactexchange (EXX) potential of time-dependent density functional theory. The EXX vertex function is constrained to be local but is expected to capture similar physics as the Hartree-Fock vertex. With the EXX vertex we then consistently unify different beyond-RPA approaches such as the various re-summations of RPA with exchange (RPAx) and the second order screened exchange (SOSEX) approximation. The theoretical analysis is supported by numerical studies on the hydrogen dimer and the electron gas, and we discuss the importance of including the vertex correction in both the screened interaction and the self energy. Finally, we give details on our implementation within the plane-wave pseudo potential framework and demonstrate the excellent performance of the different RPAx methods in describing the energetics of hydrogen and van der Waals bonds.

show abstract

Section: Technical Aspectsmentioning

confidence: 99%

Beyond the random phase approximation with a local exchange vertex

2018

View full text Add to dashboard Cite

show abstract

“…For example, TDDFT has been used to calculate C 6 coefficients of open shell atoms and ions, giving good agreement with experiment and more advanced methods. 14,33 A growing number of researchers are using TDDFT and ACFD for increasingly complex calculations 18,[25][26][27][28][29]34,35 that are not yet feasible in wavefunction methods.…”

Section: B Amentioning

confidence: 99%

Casimir–Polder Size Consistency: A Constraint Violated by Some Dispersion Theories

Gould

Toulouse

Ángyán

et al. 2017

J. Chem. Theory Comput.

Self Cite

View full text Add to dashboard Cite

A key goal in quantum chemistry methods, whether ab initio or otherwise, is to achieve size consistency. In this manuscript we formulate the related idea of "Casimir-Polder size consistency" that manifests in long-range dispersion energetics. We show that local approximations in time-dependent density functional theory dispersion energy calculations violate the consistency condition because of incorrect treatment of highly non-local "xc kernel" physics, by up to 10% in our tests on closedshell atoms.Quantum chemical approaches and electronic structure theories more generally aim to reproduce the key energetic physics of electrons with the goal of calculating energies for systems of interest. To a leading approximation two infinitely-separated quantum systems should have an energy that is given by the sum of the energies of the two components calculated separately -a feature known as size consistency. Thus, quantum chemistry methods are generally expected to reproduce this important property of quantum mechanics. Although its violation is sometimes tolerated (see e.g. Nooijen et al 1 ) for greater accuracy or lower cost, it is nonetheless broadly accepted that size consistency is an important goal in method development as it captures a fundamental property of electronic systems.The size consistency concept does not just apply at leading order, however. As two systems A and B approach each other, additional terms contribute to the energy, and these terms depend on properties of the isolated individual systems and the distance D between them. As D → ∞, the energy may thus be written aswhere the potential energydepends in some factorizable way only on local properties L X p of the isolated systems X = A, B. Thus, e.g. for systems with net local charges Q A and Q B , we have a leading term. Dipoles and higher multipoles yield similar expressions but with larger exponents p > 1 and thus decay more rapidly. These static and multipolar contributions, including the static induction energy, are present at the electrostatic level and are properly included, via the Hartree energy, in all size consistent quantum chemi-1 arXiv:1711.08727v1 [physics.chem-ph]

show abstract

“…This approach to the ground state electronic correlation energy can be seen both as a DFT approximation [16,22] or a CC approximation [23]. The RPA also has analogies with MP theory [24]. Unlike CC and MP theories, which are applied exclusively as post Hartree-Fock methods, the RPA is most often evaluated from a DFT starting point.…”

mentioning

confidence: 99%

Bridging molecular dynamics and correlated wave-function methods for accurate finite-temperature properties

Rocca

Dixit

Badawi

et al. 2019

Phys. Rev. Materials

Self Cite

View full text Add to dashboard Cite

We introduce the "selPT" perturbative approach, based on ab initio molecular dynamics (AIMD), for computing accurate finite-temperature properties by efficiently using correlated wave-function methods. We demonstrate the power of the method by computing prototypical molecular enthalpies of adsorption in zeolite (CH4 and CO2 on protonated chabazite at 300 K) using the random phase approximation. Results are in excellent agreement with experiment. The improved accuracy provided by selPT represents a crucial step towards the goal of truly quantitative AIMD prediction of experimental observables at finite temperature.

show abstract

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

Cited by 32 publications

References 60 publications

Beyond the random phase approximation with a local exchange vertex

Beyond the random phase approximation with a local exchange vertex

Casimir–Polder Size Consistency: A Constraint Violated by Some Dispersion Theories

Bridging molecular dynamics and correlated wave-function methods for accurate finite-temperature properties

Contact Info

Product

Resources

About