Exploring the Limits of the XYG3-Type Doubly Hybrid Approximations for the Main-Group Chemistry: The xDH@B3LYP Model.

Despite being the most accurate class of density functional approximations for the main-group chemistry, doubly hybrid approximations (DHAs) are generally considered to be incomplete in describing the medium- to long-range dispersive interactions. The existing DHAs are often supplemented with empirical long-range dispersion corrections. By using the extensive and chemically diverse GMTKN55 database, we explore the limits of the XYG3-type DHAs using the B3LYP reference orbitals, namely, xDH@B3LYP, with a gradually relaxed constraint on the mixing parameters of DHAs. Our results demonstrate that the xDH@B3LYP model can provide a balanced description of both covalent and noncovalent interactions with the accuracy and robustness comparable to or even better than the very expensive composite methods in wave function theory. Such an accuracy can be achieved without resorting to the use of any long-range correction scheme, shedding new light on the development of DHAs.

• Publication year

  2021

• Venue

  Journal of Physical Chemistry Letters

• Publication date

  2021-03-10

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1021/acs.jpclett.1c00360PMID 33689361
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Minimally Empirical Double-Hybrid Functionals Trained against the GMTKN55 Database: revDSD-PBEP86-D4, revDOD-PBE-D4, and DOD-SCAN-D4

  2019cited by this paper
• Simultaneous Attenuation of Both Self-Interaction Error and Nondynamic Correlation Error in Density Functional Theory: A Spin-Pair Distinctive Adiabatic-Connection Approximation.

  2019cited by this paper
• New Basis Set Exchange: An Open, Up-to-Date Resource for the Molecular Sciences Community

  2019cited by this paper
• Density functional analysis: The theory of density-corrected DFT.

  2019cited by this paper
• Range-separated hybrid density functionals made simple.

  2019cited by this paper
• Survival of the most transferable at the top of Jacob's ladder: Defining and testing the ωB97M(2) double hybrid density functional.

  2018cited by this paper
• A look at the density functional theory zoo with the advanced GMTKN55 database for general main group thermochemistry, kinetics and noncovalent interactions.

  2017cited by this paper
• Construction of a Spin-Component Scaled Dual-Hybrid Random Phase Approximation.

  2017cited by this paper
• A computationally efficient double hybrid density functional based on the random phase approximation.

  2016cited by this paper
• SCAN-based hybrid and double-hybrid density functionals from models without fitted parameters.

  2015cited by this paper
• Communication: double-hybrid functionals from adiabatic-connection: the QIDH model.

  2014cited by this paper
• Reaching a Uniform Accuracy for Complex Molecular Systems: Long-Range-Corrected XYG3 Doubly Hybrid Density Functional.

  2013cited by this paper
• Doubly hybrid density functional xDH-PBE0 from a parameter-free global hybrid model PBE0.

  2012cited by this paper
• Understanding and reducing errors in density functional calculations.

  2012cited by this paper
• Efficient and Accurate Double-Hybrid-Meta-GGA Density Functionals-Evaluation with the Extended GMTKN30 Database for General Main Group Thermochemistry, Kinetics, and Noncovalent Interactions.

  2011cited by this paper
• DSD-PBEP86: in search of the best double-hybrid DFT with spin-component scaled MP2 and dispersion corrections.

  2011cited by this paper
• Seeking for parameter-free double-hybrid functionals: the PBE0-DH model.

  2011cited by this paper
• A thorough benchmark of density functional methods for general main group thermochemistry, kinetics, and noncovalent interactions.

  2011cited by this paper
• A fast doubly hybrid density functional method close to chemical accuracy using a local opposite spin ansatz

  2011cited by this paper
• Double-hybrid density-functional theory made rigorous.

  2010cited by this paper
• Basis set consistent revision of the S22 test set of noncovalent interaction energies.

  2010cited by this paper
• Doubly hybrid density functional for accurate descriptions of nonbond interactions, thermochemistry, and thermochemical kinetics

  2009cited by this paper
• Long-range corrected double-hybrid density functionals.

  2009cited by this paper
• Semiempirical double-hybrid density functional with improved description of long-range correlation.

  2008cited by this paper
• Double-hybrid functionals for thermochemical kinetics.

  2008cited by this paper
• Improving the B3LYP bond energies by using the X1 method.

  2008cited by this paper
• Fast evaluation of scaled opposite spin second‐order Møller–Plesset correlation energies using auxiliary basis expansions and exploiting sparsity

  2007cited by this paper
• Semiempirical hybrid density functional with perturbative second-order correlation.

  2006cited by this paper
• Scaled opposite-spin second order Møller-Plesset correlation energy: an economical electronic structure method.

  2004cited by this paper
• Density-functional exchange-energy approximation with correct asymptotic behavior.

  1988cited by this paper
• Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density.

  1988cited by this paper

• UTDA-xDH: Accurate Doublet-Doublet Excitation Energies via XYG3-Type Doubly Hybrid Density Functionals within the Unrestricted Tamm-Dancoff Approximation.

  2026cites this paper
• Predicting Inverted Singlet–Triplet Gaps with XYG3-Type Doubly Hybrid Functionals

  2026cites this paper
• Reassessing DFT Rankings for Ambimodal Cycloadditions: The Impact of Accurate CCSD(T) Benchmarks and New Doubly-Hybrid Functionals.

  2026cites this paper
• Critical role of RO radicals in autocatalytic decomposition of nitrate esters

  2025cites this paper
• An Axle-Cycle Induction Strategy for the Synthesis of Chiral [2]Rotaxanes.

  2025cites this paper
• "Slim" Benchmark Sets for Faster Method Development.

  2025cites this paper
• Pair-Density Functional Theory Based on the Spin-Projected Unrestricted Hartree-Fock Method.

  2025cites this paper
• X2‐PEC: A Neural Network Model Based on Atomic Pair Energy Corrections

  2025cites this paper
• Understanding the Core Limitations of Second-Order Correlation-Based Functionals Through: Functional, Orbital, and Eigenvalue-Driven Analysis

  2025cites this paper
• Modified Opposite-Spin-Scaled Double-Hybrid Functionals

  2024cites this paper
• Identifying and embedding transferability in data-driven representations of chemical space

  2024cites this paper
• Synthesis, spectral analysis, and DFT studies of the novel pyrano[3,2-c] quinoline-based 1,3,4-thiadiazole for enhanced solar cell performance

  2024cites this paper
• How accurate can Kohn‐Sham density functional be for both main‐group and transition metal reactions

  2024cites this paper
• Toward Efficient and Unified Treatment of Static and Dynamic Correlations in Generalized Kohn–Sham Density Functional Theory

  2024cites this paper
• Regularized and Opposite Spin-Scaled Functionals from Møller-Plesset Adiabatic Connection─Higher Accuracy at Lower Cost.

  2023cites this paper
• A double-hybrid density functional based on good local physics with outstanding performance on the GMTKN55 database.

  2023cites this paper
• A semilocal machine-learning correction to density functional approximations.

  2023cites this paper
• QSAR modeling of pyrazoline derivative as carbonic anhydrase inhibitors

  2023cites this paper
• Improving XYG3-type doubly hybrid approximation using self-interaction corrected SCAN density and orbitals via the PZ-SIC framework: The xDH@SCAN(SIC) approach.

  2023cites this paper
• DFT exchange: sharing perspectives on the workhorse of quantum chemistry and materials science

  2022cites this paper
• Analytic Gradients for the Long-Range-Corrected XYG3 Type of Doubly Hybrid Density Functionals: Theory, Implementation, and Assessment.

  2022cites this paper
• Theoretical Description of Water from Single-Molecule to Condensed Phase: a Review of Recent Progress on Potential Energy Surfaces and Molecular Dynamics

  2022cites this paper
• Accurate Prediction of Nuclear Magnetic Resonance Parameters via the XYG3 Type of Doubly Hybrid Density Functionals.

  2022cites this paper
• Assessment of advanced xDH@B3LYP methods in describing various potential energy curves driven by π-π, CH/π, and SH/π non-bonded interactions

  2022cites this paper
• Assessment of DFT methods for the prediction of detachment energies and electronic structures of complex and multiply charged anions

  2021cites this paper
• Noncovalent Interactions from Models for the Møller–Plesset Adiabatic Connection

  2021cites this paper
• Doubly Hybrid Functionals Close to Chemical Accuracy for Both Finite and Extended Systems: Implementation and Test of XYG3 and XYGJ-OS

  2021cites this paper
• DeepNCI: DFT Noncovalent Interaction Correction with Transferable Multimodal Three-Dimensional Convolutional Neural Networks

  2021cites this paper
• Efficient Dynamic Computational Strategy for Heterogeneous Catalysis Based on Neural Network Potential Energy Surface: A Case Study of Temperature-Dependent Thermodynamics and Kinetics for the Chemisorbed on-surface CO

  2021cites this paper
• Does GLPT2 offer any actual benefit over conventional HF-MP2 in the context of double-hybrid density functionals?

  2021cites this paper
• Surprisingly Good Performance of XYG3 Family Functionals Using a Scaled KS-MP3 Correlation.

  2021cites this paper