Nonempirical Range-Separated Hybrid Functional with Spatially Dependent Screened Exchange DOI
Jiawei Zhan, Marco Govoni, Giulia Galli

et al.

Journal of Chemical Theory and Computation, Journal Year: 2023, Volume and Issue: 19(17), P. 5851 - 5862

Published: Aug. 17, 2023

Electronic structure calculations based on density functional theory (DFT) have successfully predicted numerous ground-state properties of a variety molecules and materials. However, exchange correlation functionals currently used in the literature, including semilocal hybrid functionals, are often inaccurate to describe electronic heterogeneous solids, especially systems composed building blocks with large dielectric mismatch. Here, we present dielectric-dependent range-separated functional, screened-exchange (SE-RSH), for investigation We define spatially dependent fraction exact inspired by static Coulomb-hole (COHSEX) approximation many-body perturbation theory, show that proposed accurately predicts several nonmetallic interfaces, three- two-dimensional, pristine, defective solids nanoparticles.

Language: Английский

Best‐Practice DFT Protocols for Basic Molecular Computational Chemistry** DOI
Markus Bursch, Jan‐Michael Mewes, Andreas Hansen

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(42)

Published: Sept. 14, 2022

Nowadays, many chemical investigations are supported by routine calculations of molecular structures, reaction energies, barrier heights, and spectroscopic properties. The lion's share these quantum-chemical applies density functional theory (DFT) evaluated in atomic-orbital basis sets. This work provides best-practice guidance on the numerous methodological technical aspects DFT three parts: Firstly, we set stage introduce a step-by-step decision tree to choose computational protocol that models experiment as closely possible. Secondly, present recommendation matrix guide choice depending task at hand. A particular focus is achieving an optimal balance between accuracy, robustness, efficiency through multi-level approaches. Finally, discuss selected representative examples illustrate recommended protocols effect choices.

Language: Английский

Citations

487
Best‐Practice DFT Protocols for Basic Molecular Computational Chemistry** DOI Creative Commons
Markus Bursch, Jan‐Michael Mewes, Andreas Hansen

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(42)

Published: Sept. 14, 2022

Abstract Nowadays, many chemical investigations are supported by routine calculations of molecular structures, reaction energies, barrier heights, and spectroscopic properties. The lion's share these quantum‐chemical applies density functional theory (DFT) evaluated in atomic‐orbital basis sets. This work provides best‐practice guidance on the numerous methodological technical aspects DFT three parts: Firstly, we set stage introduce a step‐by‐step decision tree to choose computational protocol that models experiment as closely possible. Secondly, present recommendation matrix guide choice depending task at hand. A particular focus is achieving an optimal balance between accuracy, robustness, efficiency through multi‐level approaches. Finally, discuss selected representative examples illustrate recommended protocols effect choices.

Language: Английский

Citations

97
GPAW: An open Python package for electronic structure calculations DOI Creative Commons
Jens Jørgen Mortensen, Ask Hjorth Larsen, Mikael Kuisma

et al.

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 160(9)

Published: March 7, 2024

We review the GPAW open-source Python package for electronic structure calculations. is based on projector-augmented wave method and can solve self-consistent density functional theory (DFT) equations using three different wave-function representations, namely real-space grids, plane waves, numerical atomic orbitals. The representations are complementary mutually independent be connected by transformations via grid. This multi-basis feature renders highly versatile unique among similar codes. By virtue of its modular structure, code constitutes an ideal platform implementation new features methodologies. Moreover, it well integrated with Atomic Simulation Environment (ASE), providing a flexible dynamic user interface. In addition to ground-state DFT calculations, supports many-body GW band structures, optical excitations from Bethe-Salpeter Equation, variational calculations excited states in molecules solids direct optimization, real-time propagation Kohn-Sham within time-dependent DFT. A range more advanced methods describe magnetic non-collinear magnetism also now available. addition, calculate non-linear tensors solids, charged crystal point defects, much more. Recently, support graphics processing unit (GPU) acceleration has been achieved minor modifications thanks CuPy library. end outlook, describing some future plans GPAW.

Language: Английский

Citations

84
Ab initio quantum chemistry with neural-network wavefunctions DOI
Jan Hermann,

James Spencer,

Kenny Choo

et al.

Nature Reviews Chemistry, Journal Year: 2023, Volume and Issue: 7(10), P. 692 - 709

Published: Aug. 9, 2023

Language: Английский

Citations

59
Ensemble Density Functional Theory of Ground and Excited Energy Levels DOI
Emmanuel Fromager

The Journal of Physical Chemistry A, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 20, 2025

A Kohn–Sham (KS) density-functional energy expression is derived for any (ground or excited) state within a given many-electron ensemble along with the stationarity condition it fulfills respect to density, thus giving access both physical levels and individual-state densities, in principle exactly. We also provide working equations evaluation of latter from true static density–density linear response function. Unlike Gould's recent potential functional approach excited states [arXiv:2404.12593], we use density as sole basic variable. While state-specific KS naturally emerges present formalism, at exact Hartree-exchange-only (Hx) level approximation, standard implementation orbital-optimized theory recovered when recycling regular ground-state Hx-correlation this context.

Language: Английский

Citations

2
Development and Applications of the Density-Based Theory of Chemical Reactivity DOI
Chunying Rong, Dongbo Zhao, Xin He

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2022, Volume and Issue: 13(48), P. 11191 - 11200

Published: Nov. 29, 2022

Density functional theory, which is well-recognized for its accuracy and efficiency, has become the workhorse modeling electronic structure of molecules extended materials in recent decades. Nevertheless, establishing a density-based conceptual framework to appreciate bonding, stability, function, reactivity, other physicochemical properties still an unaccomplished task. In this Perspective, we at first provide overview four pathways currently available literature tackle matter, including orbital-free density direct use density-associated quantities, information-theoretic approach. Then, highlight several advances employing these approaches realize new understandings chemical concepts such as covalent noncovalent interactions, cooperation, frustration, homochirality, chirality hierarchy, electrophilicity, nucleophilicity, regioselectivity, stereoselectivity. Finally, few possibilities future development relatively uncharted territory. Opportunities are abundant, they all ours taking.

Language: Английский

Citations

42
The quest for superheavy elements and the limit of the periodic table DOI
Odile R. Smits, Ch. E. Düllmann, P. Indelicato

et al.

Nature Reviews Physics, Journal Year: 2023, Volume and Issue: 6(2), P. 86 - 98

Published: Dec. 11, 2023

Language: Английский

Citations

33
Ultrahigh capacity and reversible hydrogen storage media based on Li-decorated T-BN monolayers DOI
Yongliang Yong, Qihua Hou, Xiaobo Yuan

et al.

Journal of Energy Storage, Journal Year: 2023, Volume and Issue: 72, P. 108169 - 108169

Published: July 6, 2023

Language: Английский

Citations

32
A Perspective on Sustainable Computational Chemistry Software Development and Integration DOI Creative Commons

Rosa Di Felice,

Maricris L. Mayes, Ryan M. Richard

et al.

Journal of Chemical Theory and Computation, Journal Year: 2023, Volume and Issue: 19(20), P. 7056 - 7076

Published: Sept. 28, 2023

The power of quantum chemistry to predict the ground and excited state properties complex chemical systems has driven development computational software, integrating advances in theory, applied mathematics, computer science. emergence new paradigms associated with exascale technologies also poses significant challenges that require a flexible forward strategy take full advantage existing forthcoming resources. In this context, sustainability interoperability software are among most pressing issues. perspective, we discuss infrastructure needs investments an eye fully utilize resources provide unique tools for next-generation science problems scientific discoveries.

Language: Английский

Citations

28
State-Specific Coupled-Cluster Methods for Excited States DOI Creative Commons
Yann Damour, Anthony Scemama, Denis Jacquemin

et al.

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(10), P. 4129 - 4145

Published: May 15, 2024

We reexamine ΔCCSD, a state-specific coupled-cluster (CC) with single and double excitations (CCSD) approach that targets excited states through the utilization of non-Aufbau determinants. This methodology is particularly efficient when dealing doubly states, domain in which standard equation-of-motion CCSD (EOM-CCSD) formalism falls short. Our goal here to evaluate effectiveness ΔCCSD applied other types comparing its consistency accuracy EOM-CCSD. To this end, we report benchmark on excitation energies computed EOM-CCSD methods for set molecular excited-state encompasses not only but also doublet–doublet transitions (singlet triplet) singly closed-shell systems. In latter case, rely minimalist version multireference CC known as two-determinant method compute states. data set, consisting 276 stemming from quest database [Véril et al., WIREs Comput. Mol. Sci. 2021, 11, e1517], provides significant base draw general conclusions concerning ΔCCSD. Except found underperforms For transitions, difference between mean absolute errors (MAEs) two methodologies (of 0.10 0.07 eV) less pronounced than obtained systems (MAEs 0.15 0.08 eV). discrepancy largely attributed greater number exhibiting multiconfigurational characters, are more challenging typically small improvements by employing optimized orbitals.

Language: Английский

Citations

16