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Ultrafast Excited-State Dynamics of Ligand-Field and Ligand-to-Metal Charge-Transfer States of CuCl<sub>4</sub><sup>2–</sup> in Solution: A Detailed Transient Absorption Studyстатья
- Авторы: Mereshchenko Andrey S., Myasnikova Olesya S., Olshin Pavel K., Matveev Sergey M., Panov Maxim S., Kochemirovsky Vladimir A., Skripkin Mikhail Yu, Tarnovsky Alexander N.
- Журнал: Journal of Physical Chemistry B
- Том: 122
- Номер: 46
- Год издания: 2018
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 10558
- Последняя страница: 10571
- DOI: 10.1021/acs.jpcb.8b06901
- Аннотация: Ultrafast excited-state dynamics of CuCl4 2- in acetonitrile is studied by femtosecond broadband transient absorption spectroscopy following excitation of the complex into all ligand-field (LF or d-d) states and into the two ligand-to-metal charge transfer (LMCT) states corresponding to the most intense steady-state absorption bands. The LF excited states are found to be nonreactive. The lowest-lying 2E LF excited state has a lifetime less than 150 fs, and the lifetimes of the second (2B1) and the third (2A1) LF excited states are 1 and 5 ps, respectively. All three LF states decay directly into the ground 2B2 state. Such significant differences in excited-state decay time constants were rationalized computationally through time-dependent density functional theory (TD-DFT) computations. TD-DFT mapping of the relaxation pathway along the symmetric Cl-Cu-Cl umbrella bending vibration gives evidence for a conical intersection between the 2E excited state and the ground 2B2 state...
- Добавил в систему: Кочемировский Владимир Алексеевич