При помощи нестационарной теории функционала плотности (TD-DFT) на уровне X3LYP/6-31++G(d,p)/SMD вычислен вибронный спектр поглощения тиазинового красителя лазурного А (Azure А, AА) в водном растворе. Данное исследование является логическим продолжением опубликованной ранее работы [L.O. Kostjukova et al. Int. J. Quantum Chem. (2021) e26662], в которой водное окружение AA задавалось неявно в приближении сплошной среды при помощи модели SMD. В настоящей работе использовалось комбинированное задание водного окружения: явным образом описывались три молекулы воды, образующие сильные водородные связи с молекулой красителя; остальная водная среда задавалась неявно, также методом SMD. Данный подход применялся с целью выяснения влияния сайт-специфических взаимодействий с растворителем как на основное, так и на возбужденное состояние молекулы красителя, и на переход между ними (сольватохромизм). Представляло интерес также и обратное влияние возбуждения молекулы AА на ее ближайшую гидратную оболочку. Расчеты показали, что имеет место усиление этих Н-связей при фотовозбуждении красителя. При этом максимум вибронного спектра поглощения AA испытывает батохромный сдвиг на 15 нм. Данные результаты проанализированы с точки зрения сольватохромной теории. Построены граничные молекулярные орбитали, между которыми происходит электронный переход, карты распределения электронной плотности и электростатического потенциала основного и возбужденного состояний системы «АА+3H2O». Выполнен анализ фотоиндуцированной поляризации молекулы красителя.
лазурный А, водный раствор, возбужденное состояние, вибронный спектр поглощения, сольватохромизм, водородная связь, нестационарная теория функционала плотности
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