The First Experimental Charge Density Studies and Comparative Periodic DFT Calculations for Crystalline Hydrogen Peroxide Adducts: Peculiarities of the HO–OH Covalent Bond

The First Experimental Charge Density Studies and Comparative Periodic DFT Calculations for Crystalline Hydrogen Peroxide Adducts: Peculiarities of the HO–OH Covalent Bond Научная публикация

Журнал

Journal of Physical Chemistry Letters
ISSN: 1948-7185

Вых. Данные

Год: 2025, Том: 16, Номер: 40, Страницы: 10316-10323 Страниц : 8 DOI: 10.1021/acs.jpclett.5c01752

Авторы

Vener Mikhail V. ¹ , Medvedev Alexander G. ¹ , Stash Adam I. ² , Mikhaylov Alexey A. ¹ , Prikhodchenko Petr V. ¹ , Baravikov Dmitry E. ¹ , Dalinger Igor L. ³ , Churakov Andrei V. ¹ , Dolgushin Fedor M. ¹

Организации

1	N.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii prosp. 31, 119991 Moscow, Russia
2	A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova St. 28, 119334 Moscow, Russia
3	N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninskii prosp. 47, 119991 Moscow, Russia

Charge density distributions in crystalline peroxosolvates of parabanic acid C3H2N2O3·0.5H2O2 and ammonium salt of 3,4,5-trinitropyrazole NH4+·C3N5O6–·0.5H2O2 derived from the high-resolution single-crystal X-ray experiments are reported with comparative periodic DFT calculations. Both multipole refinement and theoretical studies showed that the O–O bonds exhibit a (3, −1) critical point with electron density (ρb) of approximately 0.24 a.u. Experimental deformation density maps show not an accumulation but a depletion of charge density around O–O bond centers. The Laplacian values of electron density (∇2ρb) obtained from X-ray data are definitely positive and lie within 0.70–0.79 a.u. Theoretical values of ∇2ρb noticeably depend on the basis sets. They exhibit small, both positive and negative values for the modest basis sets and are around 0.3 a.u. for the pob-TZVP basis set. Thus, the O–O linkage can be considered as a specific ≪charge-shift≫ bond. The F–F bond in crystalline α-F2 exhibits similar features.

Vener M.V. , Medvedev A.G. , Stash A.I. , Mikhaylov A.A. , Prikhodchenko P.V. , Baravikov D.E. , Dalinger I.L. , Churakov A.V. , Dolgushin F.M.
The First Experimental Charge Density Studies and Comparative Periodic DFT Calculations for Crystalline Hydrogen Peroxide Adducts: Peculiarities of the HO–OH Covalent Bond
Journal of Physical Chemistry Letters. 2025. V.16. N40. P.10316-10323. DOI: 10.1021/acs.jpclett.5c01752 WOS Scopus OpenAlex

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