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E/Z photoisomerization pathway in pristine and fluorinated di(3-furyl)ethenesстатья
Статья опубликована в высокорейтинговом журнале
Статья опубликована в журнале из списка Web of Science и/или Scopus- Авторы: Sudarkova Svetlana M., Ioffe Ilya N.
- Журнал: Physical Chemistry Chemical Physics
- Том: 24
- Номер: 38
- Год издания: 2022
- Издательство: Royal Society of Chemistry
- Местоположение издательства: United Kingdom
- Первая страница: 23749
- Последняя страница: 23757
- DOI: 10.1039/d2cp02563a
- Аннотация: We report an XMCQDPT2 study of the E/Z photoisomerization in a series of fluorinated di(3-furyl)ethenes (3DFEs). Upon excitation, pristine and low-fluorinated 3DFE show conventional behavior of many diarylethenes: unhindered twisting motion toward the pyramidalized zwitterionic state where relaxation to the ground state occurs. However, deep fluorination of 3DFEs can hamper E-to-Z isomerization by giving rise to an alternative excited-state relaxation pathway: an out-of-plane motion of a ring fluorine atom. Importantly, the case of fluorinated 3DFEs reveals serious deficiencies of the popular TDDFT approach. With some commonly used exchange–correlation functionals, the alternative relaxation pathway is not reproduced and, moreover, an irrelevant ring rotation coordinate is predicted instead. Nevertheless, TDDFT remains qualitatively adequate for the E-to-Z twisting coordinate taken alone.
- Добавил в систему: Иоффе Илья Нафтольевич