Exploiting the locality of periodic subsystem density-functional theory: efficient sampling of the Brillouin zone

Genova, Alessandro; Pavanello, Michele

doi:10.1088/0953-8984/27/49/495501

Cited by 28 publications

(30 citation statements)

References 61 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, small deviations are expected due to the numerics involved. An additional effect may play a role, that is, the subsystem‐specific interlocking simulation cells that eQE uses exclusively to expand the wave functions and represent the Hamiltonian (all physical potentials are represented on the physical large grid, see References 22 and 23 for details). These cells are smaller than the physical cell, and as the molecule‐surface distance is increased, the cells may cease to overlap.…”

Section: Resultsmentioning

confidence: 99%

“…Among the available sDFT software, [ 19–21 ] the embedded Quantum ESPRESSO (eQE) software, [ 22 ] developed by us, implements sDFT and the coupled equations as shown in Equation ). It achieves almost perfect parallel scaling and has provided a quantitative model at a much reduced computational cost compared to KS‐DFT of the supersystem both for ground‐state dynamics simulations [ 23–26 ] and simulations of excited‐state dynamics. [ 27–30 ] To access excited states, we make use of the real‐time subsystem time‐dependent DFT (TDDFT) implementation in eQE, [ 28,29 ] which solves the time‐dependent Schrödinger equation within the adiabatic approximation,

([], \frac{- \nabla^{2}}{2} + v_{KS}^{I} ((), boldr, t) + v_{emb}^{I} ((), boldr, t)) ϕ_{i}^{I} ((), boldr, t) = i \frac{\partial ϕ_{i}^{I} ((), boldr, t)}{\partial t} .

…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Many‐body response of benzene at monolayer MoS₂: Van der Waals interactions and spectral broadening

Umerbekova

Pavanello

2020

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

Models of surface enhancement of molecular electronic response properties are challenging for two reasons: (a) molecule-surface interactions require a simultaneous solution of the molecular and the surface dynamic response (a daunting task), and (b) when solving for the electronic structure of the combined molecule + surface system, it is not trivial to single out the particular physical effects responsible for enhancement. To tackle this problem, in this work, we apply a formally exact decomposition of the system's response function into subsystem contributions by using subsystem density functional theory (DFT), which grants access to dynamic polarizabilities and optical spectra. In order to access information about the interactions between the subsystems, we extend a previously developed subsystem-based adiabatic connection fluctuation-dissipation theorem of DFT to separate the additive from the nonadditive correlation energy and identify the nonadditive correlation as the van der Waals interactions. As an example, we choose benzene adsorbed on monolayer MoS 2. We isolate the contributions to benzene's dynamic response arising from the interaction with the surface, and for the first time, we evaluate the enhancements to the effectiveness of C 6 coefficients as a function of benzene-MoS 2 distance and adsorption site. We also quantify the spectral broadening of the benzene's electronic excited states due to their interaction with the surface. We find that the broadening has a similar decay law with the molecule-surface distance as the leading van der Waals interactions (ie, R −6) and that the surface enhancement of dispersion interactions between benzene molecules is less than 5% but is still large enough (0.5 kcal/mol) to likely play a role in the prediction of interface morphologies. K E Y W O R D S linear response, many body dispersion, TDDFT, van der Waals 1 | INTRODUCTION AND BACKGROUND The development of accurate models of materials' interfaces is a priority for materials science and engineering. [1,2] Interfaces are key regions in energy materials such as photovoltaics [3] and photocatalysts, [4] as well as in technological applications such as field-effect transistors. [5] Models must be accurate, in the sense that they need to at least reproduce the most basic of properties involved in the function of the material. These vary depending on the applications [6,7] ; however, properties such as the contact angle in a surface-water interface, [8] thermal transport in the material, [9] and the optical response [10] are among the ones widely sought after. An accurate model enables the rational design of materials, which

show abstract

Section: Resultsmentioning

confidence: 99%

([], \frac{- \nabla^{2}}{2} + v_{KS}^{I} ((), boldr, t) + v_{emb}^{I} ((), boldr, t)) ϕ_{i}^{I} ((), boldr, t) = i \frac{\partial ϕ_{i}^{I} ((), boldr, t)}{\partial t} .

…”

Section: Introductionmentioning

confidence: 99%

Many‐body response of benzene at monolayer MoS₂: Van der Waals interactions and spectral broadening

Umerbekova

Pavanello

2020

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

show abstract

“…That is, molecular systems can be treated as nonperiodic embedded systems . In a recent work, we showed that it is possible to assign a set of k ‐points to each subsystem to sample the corresponding FBZ, and this number can be chosen according to the nature of the electronic structure of the subsystem. This finding allows us to represent each subsystem band with the smallest number of k ‐points needed to reach a target accuracy.…”

Section: Details Of the Eqe Implementationmentioning

confidence: 99%

“…We note in passing here that the theoretical and algorithmic developments in the FDE and linear‐scaling DFT communities can be quite complementary, a fact exemplified by the recent work of Andermatt et al, in which the combination of linear‐scaling DFT with FDE enabled a first‐principles‐based geometry optimization of the satellite tobacco mosaic virus in solution (a system which contains 10 000s of atoms). Quite simply put, this calculation would have remained intractable for the foreseeable future without the efficient utilization of the advances in both of these approaches.…”

Section: Introductionmentioning

confidence: 97%

eQE: An open‐source density functional embedding theory code for the condensed phase

Genova

Ceresoli

Krishtal

et al. 2017

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

In this work, we present the main features and algorithmic details of a novel implementation of the frozen density embedding (FDE) formulation of subsystem density functional theory (DFT) that is specifically designed to enable ab initio molecular dynamics (AIMD) simulations of largescale condensed-phase systems containing 1000s of atoms. This code (available at http://eqe. rutgers.edu) has been given the moniker of embedded Quantum ESPRESSO (eQE) as it is a generalization of the open-source Quantum ESPRESSO (QE) suite of programs. The strengths of eQE reside in a hierarchical parallelization scheme that allows for an efficient and fully self-consistent treatment of the electronic structure (via the addition of an additional DIIS extrapolation layer) while simultaneously exploiting the inherent symmetries and periodicities in the system (via sampling of subsystem-specific first Brillouin zones and utilization of subsystem-specific basis sets).While bulk liquids and molecular crystals are two classes of systems that exemplify the utility of the FDE approach (as these systems can be partitioned into weakly interacting subunits), we show that eQE has significantly extended this regime of applicability by outperforming standard semilocal Kohn-Sham DFT (KS-DFT) for large-scale heterogeneous catalysts with quite different layerspecific electronic structure and intrinsic periodicities. eQE features very favorable strong parallel scaling for a model system of bulk liquid water composed of 256 water molecules, which allows for a significant decrease in the overall time to solution when compared to KS-DFT. We show that eQE achieves speedups greater than one order of magnitude (>103) when performing AIMD simulations of such large-scale condensed-phase systems as: (1) | I N T R O D U C T I O NThe Kohn-Sham (KS) formulation of density functional theory (DFT) [1] is currently the most widely employed electronic structure method in the fields of chemistry, physics, and materials science. This is largely due to the fact that KS-DFT employing semilocal exchange-correlation (xc) functionals produces models of remarkable accuracy and predictive capability [2] with a relatively low associated computational cost (that in general Int J Quantum Chem. 2017;117:e25401.

show abstract

“…In the first release of eQE [26], we successfully implemented semilocal (GGA) level nonadditive functionals for both NAXC and NAKE with the following main features: (1) a scheme of parallel execution to distribute the workload across subsystems resulting in low data communication achieving high parallel efficiency, (2) ab initio molecular dynamics (AIMD), and (3) applicability to periodic systems. Many large systems currently outside KS-DFT's realm of applicability have been successfully studied by eQE [30,31,32,33,34,35,36]. eQE 2.0 is capable of deploying nonlocal and meta-GGA (mGGA) XC and NAKE functionals yielding highly accurate simulations of weakly interacting subsystems.…”

Section: Introductionmentioning

confidence: 99%

eQE 2.0: Subsystem DFT Beyond GGA Functionals

Mi,

Shao,

Genova

et al. 2021

Preprint

Self Cite

View full text Add to dashboard Cite

By adopting a divide-and-conquer strategy, subsystem-DFT (sDFT) can dramatically reduce the computational cost of large-scale electronic structure calculations. The key ingredients of sDFT are the nonadditive kinetic energy and exchange-correlation functionals which dominate it's accuracy. Even though, semilocal nonadditive functionals find a broad range of applications, their accuracy is somewhat limited especially for those systems where achieving balance between exchange-correlation interactions on one side and nonadditive kinetic energy on the other is crucial. In eQE 2.0, we improve dramatically the accuracy of sDFT simulations by (1) implementing nonlocal nonadditive kinetic energy functionals based on the LMGP family of functionals; (2) adapting Quantum ESPRESSO's implementation of rVV10 and vdW-DF nonlocal exchange-correlation functionals to be employed in sDFT simulations; (3) implementing "deorbitalized" meta GGA functionals (e.g., SCAN-L). We carefully assess the performance of the newly implemented tools on the S22-5 test set. eQE 2.0 delivers excellent interaction energies compared to conventional Kohn-Sham DFT and CCSD(T). The improved performance does not come at a loss of computational efficiency. We show that eQE 2.0 with nonlocal nonadditive functionals retains the same linear

show abstract

Exploiting the locality of periodic subsystem density-functional theory: efficient sampling of the Brillouin zone

Cited by 28 publications

References 61 publications

Many‐body response of benzene at monolayer MoS₂: Van der Waals interactions and spectral broadening

Many‐body response of benzene at monolayer MoS₂: Van der Waals interactions and spectral broadening

eQE: An open‐source density functional embedding theory code for the condensed phase

eQE 2.0: Subsystem DFT Beyond GGA Functionals

Contact Info

Product

Resources

About

Exploiting the locality of periodic subsystem density-functional theory: efficient sampling of the Brillouin zone

Cited by 28 publications

References 61 publications

Many‐body response of benzene at monolayer MoS2: Van der Waals interactions and spectral broadening

Many‐body response of benzene at monolayer MoS2: Van der Waals interactions and spectral broadening

eQE: An open‐source density functional embedding theory code for the condensed phase

eQE 2.0: Subsystem DFT Beyond GGA Functionals

Contact Info

Product

Resources

About

Many‐body response of benzene at monolayer MoS₂: Van der Waals interactions and spectral broadening

Many‐body response of benzene at monolayer MoS₂: Van der Waals interactions and spectral broadening