scholarly journals Ab Initio Quantum–Mechanical Predictions of Semiconducting Photocathode Materials

Micromachines ◽  
2021 ◽  
Vol 12 (9) ◽  
pp. 1002
Author(s):  
Caterina Cocchi ◽  
Holger-Dietrich Saßnick
Keyword(s):  
Ab Initio ◽  
Density Functional ◽  
Particle Accelerator ◽  
Quantum Mechanical ◽  
Many Body ◽  
Computational Accuracy ◽  
Electron Sources ◽  
Mechanical Methods ◽  
The Status ◽  
Many Body Perturbation Theory

Ab initio quantum–mechanical methods are well-established tools for material characterization and discovery in many technological areas. Recently, state-of-the-art approaches based on density-functional theory and many-body perturbation theory were successfully applied to semiconducting alkali antimonides and tellurides, which are currently employed as photocathodes in particle accelerator facilities. The results of these studies have unveiled the potential of ab initio methods to complement experimental and technical efforts for the development of new, more efficient materials for vacuum electron sources. Concomitantly, these findings have revealed the need for theory to go beyond the status quo in order to face the challenges of modeling such complex systems and their properties in operando conditions. In this review, we summarize recent progress in the application of ab initio many-body methods to investigate photocathode materials, analyzing the merits and the limitations of the standard approaches with respect to the confronted scientific questions. In particular, we emphasize the necessary trade-off between computational accuracy and feasibility that is intrinsic to these studies, and propose possible routes to optimize it. We finally discuss novel schemes for computationally-aided material discovery that are suitable for the development of ultra-bright electron sources toward the incoming era of artificial intelligence.

scholarly journals Electronic structure and core electron fingerprints of caesium-based multi-alkali antimonides for ultra-bright electron sources

2019 ◽  
Vol 9 (1) ◽  
Author(s):  
Caterina Cocchi ◽  
Sonal Mistry ◽  
Martin Schmeißer ◽  
Raymond Amador ◽  
Julius Kühn ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Density Functional ◽  
Cost Effective ◽  
Binding Energies ◽  
Many Body ◽  
Core Electron ◽  
Operational Conditions ◽  
Electron Sources ◽  
Level Shifts ◽  
Many Body Perturbation Theory

AbstractThe development of novel photocathode materials for ultra-bright electron sources demands efficient and cost-effective strategies that provide insight and understanding of the intrinsic material properties given the constraints of growth and operational conditions. To address this question, we propose a viable way to establish correlations between calculated and measured data on core electronic states of Cs-K-Sb materials. To do so, we combine first-principles calculations based on all-electron density-functional theory on the three alkali antimonides Cs3Sb, Cs2KSb, and CsK2Sb with x-ray photoemission spectroscopy (XPS) on Cs-K-Sb photocathode samples. Within the GW approximation of many-body perturbation theory, we obtain quantitative predictions of the band gaps of these materials, which range from 0.57 eV in Cs2KSb to 1.62 eV in CsK2Sb and manifest direct or indirect character depending on the relative potassium content. Our theoretical electronic-structure analysis also reveals that the core states of these systems have binding energies that depend only on the atomic species and their crystallographic sites, with largest shifts of the order of 2 eV and 0.5 eV associated to K 2p and Sb 3d states, respectively. This information can be correlated to the maxima in the XPS survey spectra, where such peaks are clearly visible. In this way, core-level shifts can be used as fingerprints to identify specific compositions of Cs-K-Sb materials and their relation with the measured values of quantum efficiency. Our results represent the first step towards establishing a robust connection between the experimental preparation and characterization of photocathodes, the ab initio prediction of their electronic structure, and the modeling of emission and beam formation processes.

scholarly journals General Many-Body Framework for Data-Driven Potentials with Arbitrary Quantum Mechanical Accuracy: Water as a Case Study

2021 ◽  
Author(s):  
Eleftherios Lambros ◽  
Saswata Dasgupta ◽  
Etienne Palos ◽  
Steven Swee ◽  
Jie Hu ◽  
...  
Keyword(s):  
Ab Initio ◽  
Density Functional ◽  
Water Clusters ◽  
Data Driven ◽  
Quantum Mechanical ◽  
Density Functionals ◽  
Many Body ◽  
Generalized Gradient ◽  
Systematic Analysis ◽  
Arbitrary Quantum

<div> <div> <div> <p> </p><div> <div> <div> <p>We present a general framework for the development of data-driven many-body (MB) potential energy functions (MB-QM PEFs) that represent the interactions between small molecules at an arbitrary quantum-mechanical (QM) level of theory. As a demonstration, a family of MB-QM PEFs for water are rigorously derived from density functionals belonging to differ- ent rungs across Jacob’s ladder of approximations within density functional theory (MB-DFT) as well as from Møller-Plesset perturbation theory (MB-MP2). Through a systematic analysis of individual many-body contributions to the interaction energies of water clusters, we demonstrate that all MB-QM PEFs preserve the same accuracy as the corresponding ab initio calculations, with the exception of those derived from density functionals within the generalized gradient approximation (GGA). The differences between the DFT and MB-DFT results are traced back to density-driven errors that prevent GGA functionals from accurately representing the underlying molecular interactions for different cluster sizes and hydrogen-bonding arrangements. We show that this shortcoming may be overcome, within the many-body formalism, by using density-corrected functionals that provide a more consistent representation of each individual many-body contribution. This is demonstrated through the development of a MB-DFT PEF derived from density-corrected PBE-D3 data, which more accurately reproduce the corresponding ab initio results. </p> </div> </div> </div> </div> </div> </div>

An Introduction to the Theoretical Basis of Semi-Empirical Quantum-Mechanical Methods for Biological Chemists

1998 ◽  
Author(s):  
Nigel G. J. Richards
Keyword(s):  
Nucleic Acids ◽  
Ab Initio ◽  
Density Functional ◽  
Photosynthetic Reaction Center ◽  
Quantum Mechanical ◽  
Field Methods ◽  
Mechanical Methods ◽  
Classical Models ◽  
The Many ◽  
Semi Empirical

Computational methods that can be employed to investigate fundamental questions concerning the complex chemical and structural behavior of biological molecules such as proteins, carbohydrates, and nucleic acids have been traditionally limited by the large number of atoms that comprise even the simplest system of biochemical interest. As a consequence, highly parameterized, empirical force field methods have been developed that describe the energy of macromolecular structures as a function of the spatial locations of the atomic nuclei. In combination with algorithms for simulating molecular dynamics, these classical models allow relatively accurate calculations of the structural and thermodynamic properties associated with proteins and nucleic acids. On the other hand, empirical approaches cannot be used to model molecular behavior that is directly dependent on electrons and their energies. For example, no information can be obtained concerning the electronic spectra of macromolecule/ligand complexes, electron transfer reactions such as those that occur within the photosynthetic reaction center, nitrogenase, an enzyme involved in nitrogen fixation, or cytochrome c oxidase which catalyzes the reduction of oxygen in the last step of aerobic respiration. Accurate modeling of transition states, excited states, and intermediates in biological catalysis requires application of quantummechanical (QM) representations since all of these phenomena depend on the distribution and/or excitation of electrons. At present, the most accurate ab initio algorithms for calculating electronic structure cannot be applied to systems comprised of hundreds of atoms, as such calculations scale as N4–N7 on most workstations, where N is the number of functions used in constructing the many-electron, molecular wavefunction. Even with the implementation of ab initio codes optimized for use on parallel computing engines, and density functional approaches, it is likely that high-accuracy QM calculations in the near future will remain limited to systems that comprise tens, rather than hundreds, of nonhydrogen atoms. Semi-empirical quantum-mechanical methods combine fundamental theoretical treatments of electronic behavior with parameters obtained from experiment to obtain approximate wavefunctions for molecules composed of hundreds of atoms.

scholarly journals General Many-Body Framework for Data-Driven Potentials with Arbitrary Quantum Mechanical Accuracy: Water as a Case Study

2021 ◽  
Author(s):  
Eleftherios Lambros ◽  
Saswata Dasgupta ◽  
Etienne Palos ◽  
Steven Swee ◽  
Jie Hu ◽  
...  
Keyword(s):  
Ab Initio ◽  
Density Functional ◽  
Water Clusters ◽  
Data Driven ◽  
Quantum Mechanical ◽  
Density Functionals ◽  
Many Body ◽  
Generalized Gradient ◽  
Systematic Analysis ◽  
Arbitrary Quantum

<div> <div> <div> <p> </p><div> <div> <div> <p>We present a general framework for the development of data-driven many-body (MB) potential energy functions (MB-QM PEFs) that represent the interactions between small molecules at an arbitrary quantum-mechanical (QM) level of theory. As a demonstration, a family of MB-QM PEFs for water are rigorously derived from density functionals belonging to differ- ent rungs across Jacob’s ladder of approximations within density functional theory (MB-DFT) as well as from Møller-Plesset perturbation theory (MB-MP2). Through a systematic analysis of individual many-body contributions to the interaction energies of water clusters, we demonstrate that all MB-QM PEFs preserve the same accuracy as the corresponding ab initio calculations, with the exception of those derived from density functionals within the generalized gradient approximation (GGA). The differences between the DFT and MB-DFT results are traced back to density-driven errors that prevent GGA functionals from accurately representing the underlying molecular interactions for different cluster sizes and hydrogen-bonding arrangements. We show that this shortcoming may be overcome, within the many-body formalism, by using density-corrected functionals that provide a more consistent representation of each individual many-body contribution. This is demonstrated through the development of a MB-DFT PEF derived from density-corrected PBE-D3 data, which more accurately reproduce the corresponding ab initio results. </p> </div> </div> </div> </div> </div> </div>

First-Principles Evaluation of the Potential of Borophene as a Monolayer Transparent Conductor

2017 ◽  
Author(s):  
Lyudmyla Adamska ◽  
Sridhar Sadasivam ◽  
Jonathan J. Foley ◽  
Pierre Darancet ◽  
Sahar Sharifzadeh
Keyword(s):  
First Principles ◽  
Density Functional ◽  
State Of The Art ◽  
Transparent Electrode ◽  
Visible Range ◽  
Two Dimensional ◽  
Transparent Conductor ◽  
Many Body ◽  
Functional Theory ◽  
Many Body Perturbation Theory

Two-dimensional boron is promising as a tunable monolayer metal for nano-optoelectronics. We study the optoelectronic properties of two likely allotropes of two-dimensional boron using first-principles density functional theory and many-body perturbation theory. We find that both systems are anisotropic metals, with strong energy- and thickness-dependent optical transparency and a weak (<1%) absorbance in the visible range. Additionally, using state-of-the-art methods for the description of the electron-phonon and electron-electron interactions, we show that the electrical conductivity is limited by electron-phonon interactions. Our results indicate that both structures are suitable as a transparent electrode.

scholarly journals A Review on Combination of Ab Initio Molecular Dynamics and NMR Parameters Calculations

2021 ◽  
Vol 22 (9) ◽  
pp. 4378
Author(s):  
Anna Helena Mazurek ◽  
Łukasz Szeleszczuk ◽  
Dariusz Maciej Pisklak
Keyword(s):  
Molecular Dynamics ◽  
Ab Initio ◽  
Small Amplitude ◽  
Ab Initio Molecular Dynamics ◽  
Quantum Mechanical ◽  
Time Step ◽  
Noticeable Effect ◽  
Nmr Parameters ◽  
Mechanical Methods ◽  
Simulation Time

This review focuses on a combination of ab initio molecular dynamics (aiMD) and NMR parameters calculations using quantum mechanical methods. The advantages of such an approach in comparison to the commonly applied computations for the structures optimized at 0 K are presented. This article was designed as a convenient overview of the applied parameters such as the aiMD type, DFT functional, time step, or total simulation time, as well as examples of previously studied systems. From the analysis of the published works describing the applications of such combinations, it was concluded that including fast, small-amplitude motions through aiMD has a noticeable effect on the accuracy of NMR parameters calculations.

Pros and cons of time-dependent hybrid density functional approach to optical spectra of solids: a case study of CeO2

2021 ◽  
Author(s):  
Huai-Yang Sun ◽  
Shuo-Xue Li ◽  
Hong Jiang
Keyword(s):  
First Principles ◽  
Density Functional ◽  
Computational Cost ◽  
Optical Spectra ◽  
First Principles Calculation ◽  
Many Body ◽  
Many Body Perturbation Theory ◽  
Pros And Cons ◽  
Hybrid Density Functional

Prediction of optical spectra of complex solids remains a great challenge for first-principles calculation due to the huge computational cost of the state-of-the-art many-body perturbation theory based GW-Bethe Salpeter equation...

scholarly journals Many-Body Perturbation Theory Using the Density-Functional Concept: Beyond theGWApproximation

2005 ◽  
Vol 94 (18) ◽  
Author(s):  
Fabien Bruneval ◽  
Francesco Sottile ◽  
Valerio Olevano ◽  
Rodolfo Del Sole ◽  
Lucia Reining
Keyword(s):  
Perturbation Theory ◽  
Density Functional ◽  
Many Body ◽  
Many Body Perturbation Theory ◽  
Functional Concept
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