Wydział Chemii

M. V. Vener

I. Yu. Chernyshov

A. A. Rykounov

Aleksander Filarowski

2018

Molecular Physics

116

251-262

10.1080/00268976.2017.1380860

Naukowa

Angielski

Artykuł

Crystalline HCl and CF₃SO₃H hydrates serve as excellent model systems for protonated water and perfluorosulphonic acid membranes, respectively. They contain characteristic H₃O⁺, H₅О⁺₂, H₇О⁺₃ and H₃O⁺(H₂O)₃ (the Eigen cation) structures. The properties of these cations in the crystalline hydrates of strong monobasic acids are studied by solid-state density function theory (DFT). Simultaneous consideration of the HCl and CF₃SO₃H hydrates reveals the impact of the size of a counter ion and the crystalline environment on the structure and infrared active bands of the simplest proton hydrates. The H₇O⁺₃ structure is very sensitive to the size of the counter ion and symmetry of the local environment. This makes it virtually impossible to identify the specific features of H₇O⁺₃ in molecular crystals. The H₃O⁺ ion can be treated as the Eigen-like cation in the crystalline state. Structural, infrared and electron-density features of H₅О⁺₂ and the Eigen cation are virtually insensitive to the size of the counter ion and the symmetry of the local crystalline environment. These cations can be considered as the simplest stable proton hydrates in the condensed phase. Finally, the influence of the Grimme correction on the structure and harmonic frequencies of the molecular crystals with short (strong) intermolecular O–H···O bonds is discussed.

Crystal structure databases analysis, nitric acid trihydrate, strong and moderate intermolecular H-bonds, IR active bands, electron-density features

http://doi.org/10.1080/00268976.2017.1380860