Data-Driven Improvement of Local Hybrid Functionals: Neural-Network-Based Local Mixing Functions and Power-Series Correlation Functionals

Journal of Chemical Theory and Computation, Год журнала: 2025, Номер unknown

Опубликована: Янв. 13, 2025

Local hybrid functionals (LHs) use a real-space position-dependent admixture of exact exchange (EXX), governed by local mixing function (LMF). The systematic construction LMFs has been hampered over the years lack physical constraints on their valence behavior. Here, we exploit data-driven approach and train new type "n-LMF" as relatively shallow neural network. input features are meta-GGA character, while W4-17 atomization-energy BH76 reaction-barrier test sets have used for training. Simply replacing widely "t-LMF" LH20t functional n-LMF provides LH24n-B95 functional. Augmented DFT-D4 dispersion corrections, LH24n-B95-D4 remarkably improves WTMAD-2 value large GMTKN55 suite general main-group thermochemistry, kinetics, noncovalent interactions (NCIs) from 4.55 to 3.49 kcal/mol. As found limited flexibility B95c correlation disfavor much further improvement NCIs, proceeded replace it an optimized B97c-type power-series expansion. This gives LH24n LH24n-D4 3.10 kcal/mol, so far lowest rung 4 in self-consistent calculations. perform moderately well organometallic transition-metal energetics leaving room improvements that area. Compared complete neural-network like DM21, present more tailored just LMF flexible but well-defined human-designed LH retains possibility graphical analyses gain deeper understanding. We find both recent x-LMF suppress so-called gauge problem hybrids without adding calibration required other LMFs. plots show this can be traced back values small-density region between interacting atoms NCIs n- x-LMFs low t-LMF. also trained covalent bonds deteriorating binding energies. current enables fast efficient routine calculations using n-LMFs Turbomole.

Язык: Английский

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Balancing the Contributions to the Gradient Expansion: Accurate Binding and Band Gaps with a Nonempirical Meta-GGA

Physical Review Letters, Год журнала: 2024, Номер 133(13)

Опубликована: Сен. 26, 2024

The gradient expansion has been a long-standing guide rail in density-functional theory. We here demonstrate that for exchange-correlation approximations depend on the of density and kinetic energy density, i.e., meta-generalized (meta-GGAs), there is so far unexploited degree freedom allows to shift relative weight contributions. As dependence determines derivative discontinuity, this construct meta-GGAs adhere known exact constraints, yet have new properties. with construction meta-GGA describes both electronic bonds band gaps remarkable accuracy.

Язык: Английский

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Benchmark of Density Functional Theory in the Prediction of ¹³C Chemical Shielding Anisotropies for Anisotropic Nuclear Magnetic Resonance-Based Structural Elucidation

Journal of Chemical Theory and Computation, Год журнала: 2025, Номер unknown

Опубликована: Янв. 6, 2025

Density functional theory (DFT) calculations have emerged as a powerful theoretical toolbox for interpreting and analyzing the experimental nuclear magnetic resonance (NMR) spectra of chemical compounds. While DFT has been extensively used benchmarked isotropic NMR observables, evaluation full shielding tensor, which is necessary residual shift anisotropy (RCSA), received much less attention, despite its recent applications in structural elucidation organic molecules. In this study, we present comprehensive benchmark carbon anisotropies based on coupled cluster reference tensors taken from NS372 data set. Additionally, investigate representation DFT-predicted tensors, such eigenvalues eigenvectors. Moreover, evaluated how various methods influence discrimination possible relative configurations using recently published ΔΔRCSA set structurally diverse natural products. Our findings demonstrate that accurate interpretation RCSAs configurational conformational analysis with semilocal methods, also reduce computational demands compared to hybrid functionals commonly B3LYP.

Язык: Английский

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Local hybrid alternatives to the orbital density approximation reduce the orbital dependence of self-interaction corrected DFT and the overbinding of DFT-corrected correlated wavefunctions

The Journal of Chemical Physics, Год журнала: 2025, Номер 162(11)

Опубликована: Март 18, 2025

This work presents local hybrid alternatives to the orbital density approximation employed in self-interaction corrected functional theory (SIC-DFT) and extended for use DFT-corrected correlated wavefunction approaches (CAS-DFT). When combined with standard approximate functionals, leaves SIC-DFT energies strongly dependent on unitary transforms among occupied orbitals CAS-DFT overbound. The presented here reduce both errors. are shown an underlying nondiagonal exchange–correlation hole. A preliminary extension is active–virtual correlation. These results motivate exploration of concepts CAS-DFT.

Язык: Английский

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An evaluation of local double hybrid density functionals

Chemical Physics Letters, Год журнала: 2025, Номер unknown, С. 142048 - 142048

Опубликована: Март 1, 2025

Язык: Английский

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Computational Ab Initio Approaches for Area-Selective Atomic Layer Deposition: Methods, Status, and Perspectives

Chemistry of Materials, Год журнала: 2025, Номер unknown

Опубликована: Апрель 4, 2025

Язык: Английский

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Advancing CO₂ Conversion with Cu‐LDHs: A Review of Computational and Experimental Studies

The Chemical Record, Год журнала: 2025, Номер unknown

Опубликована: Апрель 14, 2025

Abstract Layered Double Hydroxides (LDHs) are versatile materials with tuneable properties. They show promising electro‐ and photo‐catalytic activity in the activation conversion of CO 2 . Their unique properties make LDHs pivotal emerging sustainable strategies for mitigating effect emissions. However, intricate structure‐property relationship inherent to challenges their rational design. In this review, we provide a comprehensive overview both experimental computational studies about photo‐ electro‐catalytic , mainly focusing on Cu‐based systems due superior performance producing C products. We present background framework, describing essentials tools, designed support experimentalists theoreticians development tailored LDH efficient valorisation. Finally, discuss future potential advancements, emphasizing importance new synergistic experimental‐computational studies.

Язык: Английский

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Suppressing the gauge problem in local hybrid functionals without a calibration function: The choice of local mixing function

The Journal of Chemical Physics, Год журнала: 2024, Номер 161(16)

Опубликована: Окт. 23, 2024

Modern functionals based on the exact-exchange (EXX) energy density like local hybrid (LHs) or range-separated LHs have recently received additional attention due to their advantages over established when it comes balance between self-interaction errors and static-correlation errors. A possible theoretical drawback of such years has been so-called gauge problem inherent ambiguity exchange-energy densities. LH20t more sophisticated thereon constructed using suitably optimized calibration functions (CFs) minimize mismatch semi-local EXX Here, we show that unphysical contributions arising from may also be reduced significantly without a CF by tailoring position-dependence admixture (local mixing function, LMF) in way suppress spurious positive energy-density locally space. This is achieved building x-LMFs upon ratio The resulting LH24x functional provides similar accuracy, e.g., for GMTKN55 test suite, as LH20t, but introduction CF! We provide detailed comparative analyses integrated energies spatially resolved good performances chemically relevant differences are some extent core nature artifacts cancel out efficiently.

Язык: Английский

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Combining real-space and local range separation—The MH24 locally range-separated local hybrid functional

The Journal of Chemical Physics, Год журнала: 2024, Номер 161(21)

Опубликована: Дек. 3, 2024

In this work, the development of a new general-purpose exchange–correlation hybrid functional based on recent locally range-separated local approach is presented. particular, functional, denoted as MH24, combines non-empirical treatment admixture long-range exact exchange with real-space separation for exact-exchange governed by mixing function (LMF) and empirical LYP-based correlation to enable flexible description same- opposite-spin effects. The nine parameters MH24 model have been optimized using state-of-the-art super-self-consistent-field approach, which exploits sensitivity specific properties, such core ionization potentials, electron affinities, atomization energies, in regions real space LMF into core, valence, asymptotic part. functionals are shown be able simultaneously provide good accuracy valence properties well affinities noble gas dimer dissociation curves, while satisfying multiple known constraints related functionals. thus major step toward more sophisticated models.

Язык: Английский

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Towards reliable beyond-zero-sum density functional theory: Wavefunction-inspired DFT meets DFT-inspired wavefunctions

Annual reports in computational chemistry, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Язык: Английский

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