The stability of covalent dative bond significantly increases with increasing solvent polarity

Lo, Rabindranath; Manna, Debashree; Lamanec, Maximilián; Dračínský, Martin; Bouř, Petr; Wu, Tao; Bastien, Guillaume; Kaleta, Jiřı́; Miriyala, Vijay Madhav; Špirko, V.; Mašínová, Anna; Nachtigallová, Dana; Hobza, Pavel

doi:10.1038/s41467-022-29806-3

Cited by 20 publications

(29 citation statements)

References 43 publications

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“…21 The stability of covalent-bonded systems is thought to be only slightly affected by the solvent. However, in our recent study, 22 we found a surprising stabilization of covalent/dative bonding complexes that correlated with the increasing polarity of solvents. We explained this observation by transferring a charge (CT) between the donor and the acceptor of electrons which causes a significant dipole moment in the complex.…”

Section: Introductionmentioning

confidence: 49%

The unusual stability of H‐bonded complexes in solvent caused by greater solvation energy of complex compared to those of isolated fragments

Mašínová

Lamanec

et al. 2022

J Comput Chem

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Section: Introductionmentioning

confidence: 49%

The unusual stability of H‐bonded complexes in solvent caused by greater solvation energy of complex compared to those of isolated fragments

Mašínová

Lamanec

et al. 2022

J Comput Chem

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“…This indicates that the desulfurization liquid regenerated by modified chitosan powder can absorb more H 2 S in the same regeneration time, and the regeneration performance of modified chitosan powder is better compared with that of microspheres. This phenomenon may be due to the fact that the powdered catalyst has a more dispersed state and can be in full contact with the desulfurization solution (Lo et al, 2022). Due to the higher iron content and higher density of the microsphere catalyst, some of it accumulated at the bottom of the bubble tube during the regeneration process and could not fully contact the desulfurization solution.…”

Section: Catalyst Oxidation Regeneration Performance Evaluationmentioning

confidence: 99%

Heterogeneous catalytic oxidation regeneration of desulfurization-rich liquor with Fe3+ modified chitosan

Liu

Chen

et al. 2023

Front. Environ. Eng.

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To solve the problem of pipeline blockage caused by sulfur deposition in industrial gas wet oxidative desulfurization operations, this study developed an iron-modified chitosan catalyst for the catalytic oxidation regeneration of conventional wet oxidative desulfurization-rich liquids. Detailed characterization results show that Fe3+ species are successfully coordinated with the chitosan substrate. The results of desulfurization and regeneration experiments showed that the Fe3+-modified chitosan could effectively regenerate the desulfurization waste stream and remain stable in the acidic desulfurization stream. The powdered iron-based modified chitosan catalyst prepared with a mass ratio of chitosan to FeCl3 of 1:5 and glutaraldehyde of 12.5% by mass has better catalytic performance than the microbead counterpart. The regeneration performance of the catalyst was evaluated by the desulfurization performance of the regenerated desulfurization solution. The iron-based modified chitosan shows a good regeneration performance, and the loss of Fe content is less than 1.5% after five runs. This study provides an efficient way to develop cost-effective catalysts for the regeneration of wet oxidative desulfurization-rich liquids.

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“…However, despite the widespread popularity of using scaled harmonic frequency calculations in chemistry − (as evidenced by, for example, the thousands of citations for Scott and Radom), sparse benchmarking is available to guide users on appropriate model chemistry recommendations.…”

Section: Introductionmentioning

confidence: 99%

Model Chemistry Recommendations for Scaled Harmonic Frequency Calculations: A Benchmark Study

Trujillo

McKemmish

2023

J. Phys. Chem. A

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Despite the widespread popularity of scaled harmonic frequency calculations to predict experimental fundamental frequencies in chemistry, sparse benchmarking is available to guide users on the appropriate level of theory and basis set choices (model chemistry) or deep understanding of expected errors. An updated assessment of the best approach for scaling to minimize errors is also overdue. Here, we assess the performance of over 600 popular, contemporary, and robust model chemistries in the calculation of scaled harmonic frequencies, evaluating different scaling factor types and their implications in the scaled harmonic frequencies and model chemistry performance. We can summarize our results into three main findings: (1) Using modelchemistry-specific scaling factors optimized for three different frequency regions (low (<1,000 cm −1 ), mid (1,000−2,000 cm −1 ), and high (>2,000 cm −1 )) results in substantial improvements in the agreement between the scaled harmonic and experimental frequencies compared to other choices. (2) Larger basis sets and more robust levels of theory generally lead to superior performance; however, the particular model chemistry choice matters and poor choices lead to significantly reduced accuracies. (3) Outliers are expected in routine calculations regardless of the model chemistry choice. Our benchmarking results here do not consider the intensity of vibrational transitions; however, we draw upon previous benchmarking results for dipole moments that highlight the importance of diffuse functions (i.e., augmented basis sets) in high-quality intensity predictions. In terms of specific recommendations, overall, the highest accuracy model chemistries are double-hybrid density functional approximations with a non-Pople augmented triple-ζ basis set, which can produce median frequency errors down to 7.6 cm −1 (DSD-PBEP86/def2-TZVPD), which is very close to the error in the harmonic approximation, i.e., the anharmonicity error. Double-ζ basis sets should not be used with double-hybrid functionals as there is no improvement compared to hybrid functional results (unlike for doublehybrid triple-ζ model chemistries). Note that 6-311G* and 6-311+G* basis sets perform like a double-ζ basis set for vibrational frequencies. After scaling, all studied hybrid functionals with non-Pople triple-ζ basis sets will produce median errors of less than 15 cm −1 , with the best result of 9.9 cm −1 with B97-1/def2-TZVPD. Appropriate matching of double-ζ basis sets with hybrid functionals can produce high-quality results, but the precise choice of functional and basis set is more important. The B97-1, TPSS0-D3(BJ), or ωB97X-D hybrid density functionals with 6-31G*, pc-1, or pcseg-1 are recommended for fast routine calculations, all delivering median errors of 11−12 cm −1 . Note that dispersion corrections are not easily available for B97-1; given its strong performance here, we recommend these be added to major programs in coming updates.

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The stability of covalent dative bond significantly increases with increasing solvent polarity

Cited by 20 publications

References 43 publications

The unusual stability of H‐bonded complexes in solvent caused by greater solvation energy of complex compared to those of isolated fragments

The unusual stability of H‐bonded complexes in solvent caused by greater solvation energy of complex compared to those of isolated fragments

Heterogeneous catalytic oxidation regeneration of desulfurization-rich liquor with Fe3+ modified chitosan

Model Chemistry Recommendations for Scaled Harmonic Frequency Calculations: A Benchmark Study

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