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Electronic and Crystal Packing Effects in Terms of Static and Kinetic Force Field Features: Picolinic Acid N-Oxide and Methimazoleстатья
Статья опубликована в высокорейтинговом журнале
Статья опубликована в журнале из списка Web of Science и/или Scopus- Авторы: Kartashov Sergey V., Shteingolts Sergey A., Stash Adam I., Tsirelson Vladimir G., Fayzullin Robert R.
- Журнал: Crystal Growth and Design
- Том: 23
- Номер: 3
- Год издания: 2023
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 1726
- Последняя страница: 1742
- DOI: 10.1021/acs.cgd.2c01286
- Аннотация: Herein, we experimentally obtained and studied the inner-crystal scalarpotential fields and the associated vector force fields of static and kinetic nature inpicolinic acid N-oxide (PANO) and methimazole. The “through-bond” and “throughspace”electronic effects were defined and distinguished via the vector fields andconcurred with the penetration of the electron contributor’s electrostatic and kineticforce field pseudoatoms (φes- and φk-basins) into the occupier’s chemical atom (ρ-basin). A special focus was given to the dipolar N+−O− bond as well as to thethioamide N−CS and carboxylic OC−OH fragments. An unusual way of interatomic charge transfer was revealed between twononbonded hydrogen atoms [COO−]H···H[−C] in the PANO crystal. The experimental electric and kinetic force fields in themolecular crystals were compared to the theoretical ones for the free molecules and hydrogen-bonded associates, which helpedfigure out the natural consequences of the crystal packing effect. As expected, the appearance of neighboring attractors in a densecrystal packing requires zero-flux surfaces (ZFSs) emerging in the vector fields and the compression of the outer force fieldpseudoatoms of a molecule. We proposed to consider a ZFS in the kinetic force field to be a turning surface for electrons in the sensethat an electron passed through the boundary is immediately affected by the redirected force attributed to another attractor. Thestrengthening and noticeable increase observed in the covalency of the intramolecular hydrogen bond O−H···O in the PANO crystalis a direct consequence of such compression of the hydrogen atom and pseudoatoms by the inner-crystal environment. The Pauliand fermionic scalar and vector fields were applied to locate electron lone pairs and describe their involvement in noncovalentinteractions within the donor−acceptor mechanism.
- Добавил в систему: Сташ Адам Игаркович
Прикрепленные файлы
| № | Имя | Описание | Имя файла | Размер | Добавлен |
|---|---|---|---|---|---|
| 1. | Полный текст | CGD_2033_Fayzullin.pdf | 11,3 МБ | 10 февраля 2023 [adam_stash] | |
| 2. | Экспертное заключение | ekspertnoe_zaklyuchenie_Fayzullin_CGD_2023.pdf | 633,0 КБ | 10 февраля 2023 [adam_stash] |