Quasiparticle and fully self-consistent GW methods: An unbiased analysis using Gaussian orbitals DOI
Gaurav Harsha, Vibin Abraham, Ming Wen

et al.

Physical review. B./Physical review. B, Journal Year: 2024, Volume and Issue: 110(23)

Published: Dec. 20, 2024

We present a comparison of various approximations to the self-consistent GW methods, including one-shot G0W0 method, different quasiparticle schemes, and fully (scGW) approach. To ensure an unbiased equitable comparison, we have implemented all schemes with same underlying Matsubara formalism, while employing Gaussian orbitals describe system. Aiming assess compare analyze band gaps in semiconductors insulators, as well ionization potentials molecules. Our findings reveal that for solids, perform very similarly. However, molecules, full self-consistency outperforms other approximations, i.e., methods. work highlights importance implementation details when comparing By state-of-the-art self-consistent, finite temperature calculations, successfully addressed discrepancies existing literature regarding its performance. results also indicate stringent thresholds are imposed, scGW method consistently yields accurate results. locked icon Physics Subject Headings (PhySH)Band gapElectronic structure atoms & moleculesGW methodGreen's function methods

Language: Английский

Beyond Quasi-Particle Self-Consistent GW for Molecules with Vertex Corrections DOI Creative Commons
A. Förster

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 11, 2025

We introduce the ΣBSE@LBSE self-energy in quasi-particle self-consistent GW (qsGW) framework (qsΣBSE@LBSE). Here, L is two-particle response function, which we calculate by solving Bethe–Salpeter equation with static, first-order kernel. The same kernel added to Σ directly. For a set of medium organic molecules, show that including vertex both and crucial. This approach retains good performance qsGW for predicting first ionization potentials fundamental gaps, while it greatly improves description electron affinities. Its places qsΣBSE@LBSE among best-performing propagator methods charged excitations. Adding only, as commonly done solid-state community, leads devastating results affinities gaps. also test BSE@qsGW neutral charge-transfer excitation find perform similar. conclude promising approximation electronic beyond GW. hope future research on dynamical effects, second-order corrections, full self-consistency will improve accuracy this method, energies.

Language: Английский

Citations

1
Joint approximate diagonalization approach to quasiparticle self-consistent GW calculations DOI
Ivan Duchemin, Xavier Blase

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(5)

Published: Feb. 7, 2025

We introduce an alternative route to quasiparticle self-consistent GW calculations (qsGW) on the basis of a joint approximate diagonalization one-body Green’s functions G(εnQP) taken at input energies. Such approach allows working with full dynamical self-energy, without approximating latter by symmetrized static form as in standard qsGW scheme. Calculations GW100 molecular test set lead, nevertheless, good agreement, 60 meV mean-absolute-error accuracy ionization potential, respect conventional approach. show further that constructing density matrix from function fully scGW scheme, and not occupied orbitals, obtaining scheme intermediate between approaches, closer coupled-cluster reference values.

Language: Английский

Citations

0
Algebraic Diagrammatic Construction Theory of Charged Excitations with Consistent Treatment of Spin–Orbit Coupling and Dynamic Correlation DOI
Rajat Majumder, Alexander Yu. Sokolov

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 20, 2025

We present algebraic diagrammatic construction theory for simulating spin-orbit coupling and electron correlation in charged electronic states photoelectron spectra. Our implementation supports Hartree-Fock multiconfigurational reference wave functions, enabling efficient correlated calculations of relativistic effects using single-reference (SR-) multireference-algebraic (MR-ADC). combine the SR- MR-ADC methods with three flavors two-component Hamiltonians benchmark their performance a variety atoms small molecules. When multireference are not important, SR-ADC approximations competitive accuracy to MR-ADC, often showing closer agreement experimental results. However, character nonequilibrium regions potential energy surfaces, more reliable, predicting accurate excitation energies zero-field splittings. results demonstrate that ADC promising approaches interpreting modern spectroscopies.

Language: Английский

Citations

0
Performance of the Bethe–Salpeter Equation for Electronic Excitations in First-Row Transition Metal Complexes DOI

Florian Bogdain,

Oliver Kuehn

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: April 28, 2025

The performance of the Green's function-Bethe-Salpeter Equation (BSE@GW) approach has been systematically tested on a series first-row transition metal complexes. Special attention was paid to interplay between metal-centered (MC) and charge transfer (CT) transitions their ordering in excited singlet triplet state manifolds. Here, commonly used time-dependent density functional theory (DFT) reaches its limits particular shows strong dependence exchange-correlation functional. In contrast, present BSE@GW ultraviolet-visible (UV-vis) spectra show good agreement with experimental results as far absorption assignment are concerned. This is achieved independently underlying initial guess GW iteration. These conclusions drawn basis an investigation test set including nearly pure MC triazacyclononane different centers mixed MC-CT Fe(II) complexes numbers N-heterocyclic carbene ligands. Furthermore, important aspects calculations such ground equilibrium geometry or influence Tamm-Dancoff approximation highlighted.

Language: Английский

Citations

0
Green/WeakCoupling: Implementation of fully self-consistent finite-temperature many-body perturbation theory for molecules and solids DOI
Sergei Iskakov, Chia-Nan Yeh, Pavel Pokhilko

et al.

Computer Physics Communications, Journal Year: 2024, Volume and Issue: unknown, P. 109380 - 109380

Published: Sept. 1, 2024

Language: Английский

Citations

3
Tensor hypercontraction for fully self-consistent imaginary-time GF2 and GWSOX methods: Theory, implementation, and role of the Green’s function second-order exchange for intermolecular interactions DOI
Pavel Pokhilko, Chia-Nan Yeh, Miguel A. Morales

et al.

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(8)

Published: Aug. 26, 2024

We present an efficient MPI-parallel algorithm and its implementation for evaluating the self-consistent correlated second-order exchange term (SOX), which is employed as a correction to fully GW scheme called scGWSOX (GW plus SOX iterated achieve full Green’s function self-consistency). Due application of tensor hypercontraction (THC) in our computational procedure, scaling evaluation reduced from O(nτnAO5) O(nτN2nAO2). This THC-adapted approach enabled us conduct largest calculations with over 1100 atomic orbitals only negligible errors attributed THC fitting. Utilizing scGW, scGF2, scGWSOX, we evaluated energies intermolecular interactions. allowed circumvent issues related reference dependence ambiguity energy evaluation, are common challenges non-self-consistent calculations. demonstrate that scGW exhibits slight overbinding tendency large systems, contrary underbinding observed RPA. Conversely, such systems. behavior both physical systematic caused by exclusion-principle violating diagrams or corresponding corrections. Our analysis elucidates role played these different diagrams, crucial construction rigorous, accurate, methods. Finally, explicitly show all perturbative methods size-extensive size-consistent.

Language: Английский

Citations

1
Quasiparticle and fully self-consistent GW methods: An unbiased analysis using Gaussian orbitals DOI
Gaurav Harsha, Vibin Abraham, Ming Wen

et al.

Physical review. B./Physical review. B, Journal Year: 2024, Volume and Issue: 110(23)

Published: Dec. 20, 2024

We present a comparison of various approximations to the self-consistent GW methods, including one-shot G0W0 method, different quasiparticle schemes, and fully (scGW) approach. To ensure an unbiased equitable comparison, we have implemented all schemes with same underlying Matsubara formalism, while employing Gaussian orbitals describe system. Aiming assess compare analyze band gaps in semiconductors insulators, as well ionization potentials molecules. Our findings reveal that for solids, perform very similarly. However, molecules, full self-consistency outperforms other approximations, i.e., methods. work highlights importance implementation details when comparing By state-of-the-art self-consistent, finite temperature calculations, successfully addressed discrepancies existing literature regarding its performance. results also indicate stringent thresholds are imposed, scGW method consistently yields accurate results. locked icon Physics Subject Headings (PhySH)Band gapElectronic structure atoms & moleculesGW methodGreen's function methods

Language: Английский

Citations

0