Defect Calculation by Combined SCAN and Hybrid Functional in γ-CsPbI3

2022 ◽  
Author(s):  
Shengyuan Wang ◽  
Kin Fai Tse ◽  
Alena Boyko ◽  
Junyi Zhu
Keyword(s):  
Solar Cells ◽  
Hybrid Functional ◽  
Quantitative Understanding ◽  
Hybrid Functionals

γ-CsPbI3 solar cells have achieved promising efficiencies, yet the quantitative understanding of their defect properties is limited due to severe computational challenges of hybrid functionals. We have discovered an algorithm...

scholarly journals Exact Generalized Kohn-Sham Theory for Hybrid Functionals

2019 ◽  
Author(s):  
Rachel Garrick ◽  
Amir Natan ◽  
Tim Gould ◽  
Leeor Kronik
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
State Density ◽  
Hybrid Functional ◽  
Functional Theory ◽  
Hybrid Functionals ◽  
The Many ◽  
Ground State Density ◽  
Equivalent Description

p.p1 {margin: 0.0px 0.0px 0.0px 0.0px; line-height: 18.0px; font: 15.8px Helvetica; color: #000000; -webkit-text-stroke: #000000; background-color: #ffffff} span.s1 {font-kerning: none} span.s2 {font-kerning: none; color: #000000} <p>Hybrid functionals have proven to be of immense practical value in density functional theory calculations. While they are often thought to be a heuristic construct, it has been established that this is in fact not the case. Here, we present a rigorous and formally exact generalized Kohn-Sham (GKS) density functional theory of hybrid functionals, in which exact remainder exchange-correlation potentials combine with a fraction of Fock exchange to produce the correct ground state density. Specifically, we generalize the well-known adiabatic con- nection theorem to the case of exact hybrid functional theory and use it to provide a rigorous distinction between multiplicative exchange and correlation components. We examine the exact theory by inverting reference electron densities to obtain exact GKS potentials for hybrid functionals, showing that an equivalent description of the many-electron problem is obtained with any arbitrary global fraction of Fock exchange. We establish the dependence of these exact components on the fraction of Fock exchange and use the observed trends to shed new light on the results of approximate hybrid functional calculations.</p>

scholarly journals Exact Generalized Kohn-Sham Theory for Hybrid Functionals

2020 ◽  
Author(s):  
Rachel Garrick ◽  
Amir Natan ◽  
Tim Gould ◽  
Leeor Kronik
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Formal Theory ◽  
Density Functional Theory Calculations ◽  
State Density ◽  
Hybrid Functional ◽  
Functional Theory ◽  
Exchange Correlation ◽  
Hybrid Functionals ◽  
The Many

Hybrid functionals have proven to be of immense practical value in density functional theory calculations. While they are often thought to be a heuristic construct, it has been established that this is in fact not the case. Here, we present a rigorous and formally exact analysis of generalized Kohn-Sham (GKS) density functional theory of hybrid functionals, in which exact remainder exchange-correlation potentials combine with a fraction of Fock exchange to produce the correct ground state density. First, we extend formal GKS theory by proving a generalized adiabatic connection theorem. We then use this extension to derive two different definitions for a rigorous distinction between multiplicative exchange and correlation components - one new and one previously postulated. We examine their density-scaling behavior and discuss their similarities and differences. We then present a new algorithm for obtaining exact GKS potentials by inversion of accurate reference electron densities and employ this algorithm to obtain exact potentials for simple atoms and ions. We establish that an equivalent description of the many-electron problem is indeed obtained with any arbitrary global fraction of Fock exchange and we rationalize the Fock-fraction dependence of the computed remainder exchange-correlation potentials in terms of the new formal theory. Finally, we use the exact theoretical framework and numerical results to shed light on the exchange-correlation potential used in approximate hybrid functional calculations and to assess the consequences of different choices of fractional exchange.<br><br>

scholarly journals Optimization of a Range-Separated UW12 Hybrid Functional

2021 ◽  
Author(s):  
Zack Williams ◽  
Frederick Manby
Keyword(s):  
Power Series ◽  
Density Functional ◽  
Power Series Expansion ◽  
Correlation Model ◽  
Hybrid Functional ◽  
Main Group Chemistry ◽  
Self Consistent ◽  
Hybrid Functionals ◽  
Survival Of The Fittest ◽  
Hybrid Density Functional

In a previous paper we presented a new hybrid functional B-LYP-osUW12-D3(BJ) containing the Unsöld-w12 (UW12) hybrid correlation model. In this paper we present a new 15-parameter range-separated hybrid density functional using a power series expansion together with UW12 correlation. This functional is optimised using the survival of the fittest strategy developed for the ωB97X-V functional, fitted to data from the Main Group Chemistry Database (MGCDB84). In addition we optimize a standard hybrid and double hybrid using the same method. We show that our fully self-consistent UW12 hybrid functional WM21-D3(BJ) outperforms both of these functionals and other range-separated hybrid functionals.

scholarly journals A Review of Density Functional Models for the Description of Fe(II) Spin-Crossover Complexes

Molecules ◽  
2020 ◽  
Vol 25 (21) ◽  
pp. 5176
Author(s):  
Anton Römer ◽  
Lukas Hasecke ◽  
Peter Blöchl ◽  
Ricardo A. Mata
Keyword(s):  
Density Functional ◽  
Spin Crossover ◽  
Structure Theory ◽  
Ligand Field ◽  
Local Version ◽  
Hybrid Functional ◽  
Display Devices ◽  
Explicitly Correlated ◽  
Hybrid Functionals ◽  
The Right

Spin-crossover (SCO) materials have for more than 30 years stood out for their vast application potential in memory, sensing and display devices. To reach magnetic multistability conditions, the high-spin (HS) and low-spin (LS) states have to be carefully balanced by ligand field stabilization and spin-pairing energies. Both effects could be effectively modelled by electronic structure theory, if the description would be accurate enough to describe these concurrent influences to within a few kJ/mol. Such a milestone would allow for the in silico-driven development of SCO complexes. However, so far, the ab initio simulation of such systems has been dominated by general gradient approximation density functional calculations. The latter can only provide the right answer for the wrong reasons, given that the LS states are grossly over-stabilized. In this contribution, we explore different venues for the parameterization of hybrid functionals. A fitting set is provided on the basis of explicitly correlated coupled cluster calculations, with single- and multi-dimensional fitting approaches being tested to selected classes of hybrid functionals (hybrid, range-separated, and local hybrid). Promising agreement to benchmark data is found for a rescaled PBE0 hybrid functional and a local version thereof, with a discussion of different atomic exchange factors.

scholarly journals A Review of Density Functional Models for the Description of Fe(II) Spin Crossover Complexes

2020 ◽  
Author(s):  
Anton Römer ◽  
Lukas Hasecke ◽  
Peter Blöchl ◽  
Ricardo A. Mata
Keyword(s):  
Density Functional ◽  
Spin Crossover ◽  
Structure Theory ◽  
Ligand Field ◽  
Local Version ◽  
Hybrid Functional ◽  
Explicitly Correlated ◽  
Atomic Exchange ◽  
Hybrid Functionals ◽  
The Right

Spin crossover (SCO) complexes are in the forefront of image, memory and sensing devices, with applications already established since for thirty years. In order to reach magnetic multistability conditions, the high-spin (HS) and low-spin (LS) states have to be carefully balanced by ligand field stabilization and spin pairing energies. Both of these effects could be effectively modelled by electronic structure theory, if the description would be accurate enough to describe these concurrent influences to within a few kJ/mol. Such a milestone would allow for the in silico-driven development of SCO complexes. However, so far, the ab initio simulation of such systems has been dominated by general gradient approximation density functional calculations. The latter can only provide the right answer for the wrong reasons, given that the LS states are grossly stabilized. In this contribution, we explore different venues for the parameterisation of hybrid functionals. A fitting set is provided on the basis of explicitly correlated coupled cluster calculations, with single- and multi-dimensional fitting approaches being tested to selected classes of hybrid functionals (hybrid, range separated and local hybrid). Promising agreement to benchmark data is found for a rescaled PBE0 hybrid functional and a local version thereof, with a discussion of different atomic exchange factors.

scholarly journals Benchmark study of the performance of density functional theory for reduction potentials of vanadium compounds

2020 ◽  
pp. 14-21
Author(s):  
Samat Tussupbayev ◽  
Gulnar Kudaibergenova
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Vanadium Redox Flow Battery ◽  
Hybrid Functional ◽  
Vanadium Compounds ◽  
Functional Theory ◽  
Hartree Fock ◽  
Benchmark Study ◽  
Reduction Potentials ◽  
Hybrid Functionals

A systematic benchmark study was performed for the first time to investigate the performance of density functional theory for calculation of reduction potentials of vanadium compounds. Six density functionals of different types were selected for testing: local OLYP and M06L, global hybrid O3LYP and B3LYP, as well as, meta-hybrid functionals TPSSh and M06. Local and hybrid functionals with a relatively high contribution of Hartree-Fock exchange showed unsatisfactory results. In particular, the widely used hybrid functional B3LYP for the transformation VIII→VII occurring in the vanadium redox flow battery yields a negative value of the standard potential instead of a positive one. Among the tested functionals the smallest deviation from the experimental data provides the meta-hybrid functional TPSSh with a 10% contribution of the Hartree-Fock exchange. The computational protocol to calculate redox potentials of vanadium compounds is suggested.

Are the Current Models Helpful to Understanding Staebler-Wronski Degradation?

2004 ◽  
Vol 808 ◽  
Author(s):  
Bolko von Roedern
Keyword(s):  
Experimental Data ◽  
Solar Cells ◽  
Physical Process ◽  
Bond Breaking ◽  
Experimental Stress ◽  
Recovery Mechanisms ◽  
Quantitative Understanding ◽  
Fundamental Physical

ABSTRACTThis contribution reviews the compatibility of Staebler-Wronski models with experimental data and observations. The review will show that neither the “bond-breaking models” (originally proposed by Dersch and Stutzmann) nor the “defect conversion” models (originally proposed by Adler) can explain all observations on films and/or solar cells. It has been well accepted for some time that experimental stress and recovery phenomena, both on films and devices, always identify both “slow” and “fast” degradation and recovery mechanisms. It is argued that the quintessential understanding of the Staebler-Wronski mechanisms will come from identifying a fundamental physical process that provides a quantitative understanding of the “coupling” between the slow and fast mechanisms.

scholarly journals Fast, Accurate Enthalpy Differences in Spin Crossover Crystals from DFT+U

2020 ◽  
Author(s):  
Miriam Ohlrich ◽  
Ben Powell
Keyword(s):  
Density Functional ◽  
Spin Crossover ◽  
Mean Absolute Error ◽  
Computational Cost ◽  
Absolute Error ◽  
Hybrid Functional ◽  
Dft Methods ◽  
Temperature State ◽  
Potential Applications ◽  
Hybrid Functionals

<div>Spin crossover materials are bi-stable systems with potential applications as molecular scale electronic switches, actuators, thermometers, barometers and displays. However, calculating the enthalpy difference, DH, between the high spin (HS) and low spin (LS) states has been plagued with difficulties. For example, many common density functional theory (DFT) methods fail to even predict the correct sign of DH, which determines the low temperature state. Here, we study a collection of Fe(II) and Fe(III) materials, where DH has been measured, and which has previously been used to benchmark density functionals. The best performing hybrid functional, TPSSh, achieves a mean absolute error compared to experiment of 11 kJ/mol for this set of materials. However, hybrid functionals scale badly in the solid state; therefore, local functionals are preferable for studying crystalline materials, where the most interesting SCO phenomena occur. We show that both the Liechtenstein and Dudarev DFT+U methods are a little more accurate than TPSSh. The Dudarev method yields a mean absolute error of 8 kJ/mol for U<sub>eff</sub>=1.6 eV. However, the MAE for both TPSSh and DFT+U are dominated by a single material - if this is excluded from the set then DFT+U achieves chemical accuracy. Thus, DFT+U is an attractive option for calculating the properties of spin crossover crystals, as its accuracy is comparable to that of meta-hybrid functionals, but at a much lower computational cost.</div>

scholarly journals Exact Generalized Kohn-Sham Theory for Hybrid Functionals

2020 ◽  
Author(s):  
Rachel Garrick ◽  
Amir Natan ◽  
Tim Gould ◽  
Leeor Kronik
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Formal Theory ◽  
Density Functional Theory Calculations ◽  
State Density ◽  
Hybrid Functional ◽  
Functional Theory ◽  
Exchange Correlation ◽  
Hybrid Functionals ◽  
The Many

Hybrid functionals have proven to be of immense practical value in density functional theory calculations. While they are often thought to be a heuristic construct, it has been established that this is in fact not the case. Here, we present a rigorous and formally exact analysis of generalized Kohn-Sham (GKS) density functional theory of hybrid functionals, in which exact remainder exchange-correlation potentials combine with a fraction of Fock exchange to produce the correct ground state density. First, we extend formal GKS theory by proving a generalized adiabatic connection theorem. We then use this extension to derive two different definitions for a rigorous distinction between multiplicative exchange and correlation components - one new and one previously postulated. We examine their density-scaling behavior and discuss their similarities and differences. We then present a new algorithm for obtaining exact GKS potentials by inversion of accurate reference electron densities and employ this algorithm to obtain exact potentials for simple atoms and ions. We establish that an equivalent description of the many-electron problem is indeed obtained with any arbitrary global fraction of Fock exchange and we rationalize the Fock-fraction dependence of the computed remainder exchange-correlation potentials in terms of the new formal theory. Finally, we use the exact theoretical framework and numerical results to shed light on the exchange-correlation potential used in approximate hybrid functional calculations and to assess the consequences of different choices of fractional exchange.<br><br>

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