Towards Accurate Quantum Mechanical Thermochemistry: (1) Extensible Implementation and Comparison of Bond Additivity Corrections and Isodesmic Reactions DOI Creative Commons
Haoyang Wu, A. Mark Payne, Hao‐Wei Pang

et al.

Published: April 22, 2024

Obtaining accurate enthalpies of formation chemical species, Hf, often requires empirical corrections that connect the results quantum mechanical (QM) calculations with experimental elements in their standard state. One approach is to use atomization energy (AECs) followed by bond additivity (BACs), such as those defined Petersson et al. or Anantharaman and Melius. Another utilize isodesmic reactions (IDRs) shown Buerger We implement both approaches Arkane, an open-source software can calculate species thermochemistry using from various QM packages. In this work, we collect 421 reference literature derive Hf corrections, fit AECs BACs for 15 commonly used model chemistries. find types yield similar accuracy, although Melius-type appear generalize better. Furthermore, tend achieve better accuracy than IDRs chemistries, be less robust because sensitivity chosen reactions. Overall, are our recommended achieving enthalpies.

Language: Английский

Toward Accurate Quantum Mechanical Thermochemistry: (1) Extensible Implementation and Comparison of Bond Additivity Corrections and Isodesmic Reactions DOI Creative Commons
Haoyang Wu, A. Mark Payne, Hao‐Wei Pang

et al.

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: 128(21), P. 4335 - 4352

Published: May 16, 2024

Obtaining accurate enthalpies of formation chemical species, Δ

Language: Английский

Citations

4
Transforming PFAS management: A critical review of machine learning applications for enhanced monitoring and treatment DOI
Md Hasan-Ur Rahman,

Rabbi Sikder,

Tanvir Ahamed Tonmoy

et al.

Journal of Water Process Engineering, Journal Year: 2025, Volume and Issue: 70, P. 106941 - 106941

Published: Jan. 15, 2025

Language: Английский

Citations

0
Toward Accurate Quantum Mechanical Thermochemistry: (2) Optimal Methods for Enthalpy Calculations from Comprehensive Benchmarks of 284 Model Chemistries DOI
Haoyang Wu, Anna C. Doner, Hao‐Wei Pang

et al.

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

Published: April 20, 2025

Accurate and efficient computations of the standard enthalpies formation (ΔHf°) for small organic molecules are crucial diverse chemical engineering scientific applications. Building on part 1 this work [J. Phys. Chem. A 2024, 128, 21, 4335-4352], we systematically benchmark 284 model chemistries ΔHf° computations. These methods span semiempirical approaches, density functional theory (DFT), wave function theory, composite schemes. We derive Petersson- Melius-type bond-additivity corrections (BACs) each method using a curated database 421 reference species. further validate top-performing an independent test set 500 species, including ions, radicals, other challenging cases. Across nearly all BACs significantly improve accuracy, especially neutral singlet Composite schemes coupling moderate-level DFT geometries with local coupled-cluster single-point energies strike excellent balance between cost often approaching accuracy (≤1 kcal/mol). Notably, DLPNO-CCSD(T)-F12d/cc-pVTZ-F12//ωB97X-D/def2-TZVPD Petersson BAC attains benchmark-best mean absolute error (MAE) 0.57 kcal/mol. Switching to DLPNO-CCSD(T)-F12d/cc-pVDZ-F12//GFN2-xTB reduces computational by order magnitude, only modest increase in MAE (0.96 Although carefully tuned can also benefit charged open-shell scarcity robust data these areas highlights need broader, high-accuracy thermochemistry datasets. Overall, provides practical guidance selecting optimal efficiently compute accurate under varied constraints molecular complexities, laying foundation large-scale, high-throughput thermochemical calculations that will support data-driven discovery industrial

Language: Английский

Citations

0
Trace Adsorptive Removal of PFAS from Water by Optimizing the UiO‐66 MOF Interface DOI Creative Commons
Nebojša Ilić,

Kui Tan,

Felix Mayr

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 21, 2024

Abstract The confluence of pervasiveness, bioaccumulation, and toxicity in freshwater contaminants presents an environmental threat second to none. Exemplifying this trifecta, per‐ polyfluoroalkyl substances (PFAS) present alarming hazard among the emerging contaminants. State‐of‐the‐art PFAS adsorbents used drinking water treatment, namely, activated carbons ion‐exchange resins, are handicapped by low adsorption capacity, competitive adsorption, and/or slow kinetics. To overcome these shortcomings, metal–organic frameworks (MOFs) with tailored pore size, surface, chemistry promising alternatives. Thanks compositional modularity MOFs polymer–MOF composites, herein we report on a series water‐stable zirconium carboxylate their low‐cost polymer‐grafted composites as C 8 –PFAS benchmark kinetics “parts per billion” removal efficiencies. Bespoke insights into structure–function relationships obtained leveraging interfacial design principles solid sorbents, creating synergy between extrinsic particle surfaces intrinsic molecular building blocks.

Language: Английский

Citations

3
Unifying thermochemistry concepts in computational heterogeneous catalysis DOI Creative Commons
Bjarne Kreitz, Gabriel S. Gusmão, Dingqi Nai

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 29, 2024

Thermophysical properties of adsorbates and gas-phase species define the free energy landscape heterogeneously catalyzed processes are pivotal for an atomistic understanding catalyst performance.

Language: Английский

Citations

2
Association Kinetics for Perfluorinated n-Alkyl Radicals DOI
Hrishikesh Ram, Yuri Georgievskii, Sarah N. Elliott

et al.

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 31, 2024

Radical-radical reaction channels are important in the pyrolysis and oxidation chemistry of perfluoroalkyl substances (PFAS). In particular, unimolecular dissociation reactions within unbranched

Language: Английский

Citations

1
Towards Accurate Quantum Mechanical Thermochemistry: (1) Extensible Implementation and Comparison of Bond Additivity Corrections and Isodesmic Reactions DOI Creative Commons
Haoyang Wu, A. Mark Payne, Hao‐Wei Pang

et al.

Published: April 22, 2024

Obtaining accurate enthalpies of formation chemical species, Hf, often requires empirical corrections that connect the results quantum mechanical (QM) calculations with experimental elements in their standard state. One approach is to use atomization energy (AECs) followed by bond additivity (BACs), such as those defined Petersson et al. or Anantharaman and Melius. Another utilize isodesmic reactions (IDRs) shown Buerger We implement both approaches Arkane, an open-source software can calculate species thermochemistry using from various QM packages. In this work, we collect 421 reference literature derive Hf corrections, fit AECs BACs for 15 commonly used model chemistries. find types yield similar accuracy, although Melius-type appear generalize better. Furthermore, tend achieve better accuracy than IDRs chemistries, be less robust because sensitivity chosen reactions. Overall, are our recommended achieving enthalpies.

Language: Английский

Citations

1