Аннотация

Постоянно растущие возможности вычислительных систем и алгоритмов делают применение первопринципных методов одним из ключевых для исследования биологически активных соединений и анализа сложных механизмов их функционирования в живых организмах, а также целенаправленного поиска и прогнозирования новых форм. Целью исследования являлось определение структурных параметров и основных электронных и колебательных характеристик кристаллических галогенидов ацетилхолина (ACh-Hal).
Объектами исследования являлись хлорид и бромид ацетилхолина. Для их теоретического анализа применялись методы, основанные на теории функционала плотности (DFT) с использованием градиентных обменно-корреляционных функционалов (PBE) и полуэмпирической схемы учета дисперсионных взаимодействий (DFT+D3).
В результате выполненных расчетов для ACh-Hal были установлены оптимизированные параметры кристаллической решетки, равные a = 9,765 Å, b = 15,217 Å, c = 6,274 Å для орторомбического хлорида ацетилхолина (ACh-Cl) и a = 10,883 Å, b = 13,304 Å, c = 7,077 Å, 109,21° для моноклинного бромида (ACh-Br), а также координаты атомов и значения длин связей, валентных и торсионных углов. Анализ электронной структуры показывает, что ACh-Hal является диэлектриком с шириной запрещенной зоны 4,734 и 4,405 эВ, а эффективные заряды атомов углерода сильно анизотропны. Расчетные колебательные спектры хорошо согласуются с экспериментальными данными во всем интервале частот. Зависимость от массы аниона наиболее заметна в области решеточных колебаний.
Применение первопринципной схемы DFT+D3 позволяет получать для сложных органических биологически активных систем надежные данные об их основных свойствах.

Ключевые слова

Ацетилхолин, теория функционала плотности, дисперсионные поправки, кристаллическая и электронная структура, колебательные моды

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