期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 18, 期 11, 页码 7641-7650出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5cp06861d
关键词
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资金
- CAS 100 Talent Project
- NSFC [91233106, 21503249, 21543008]
- Natural Science Foundation of Shandong Province for Distinguished Young Scholars [JQ201103]
- Natural Science Foundation of Shandong Province for Young Scientist [ZR2015BQ010]
The ultrafast photoinduced structural change dynamics of a prototypical Cu(I) complex, namely, [Cu(dmp)(2)](+) (dmp = 2,9-dimethyl-1,10-phenanthroline), is investigated based on the theoretical analysis of static and dynamical calculations at the all-atomic level. This work mainly focuses on the intriguing structural flattening features of [Cu(dmp)(2)](+) occurring in the metal-to-ligand charge transfer singlet excited state ((MLCT)-M-1) on the sub-picosecond timescale. Our estimated time constant (similar to 675 fs) of this flattening'' motion is in good agreement with recent experimental values. The full-dimensional excited-state nonadiabatic dynamic simulation provides a direct view of the ultrafast photoinduced events of [Cu(dmp)(2)](+), especially, the structural flattening mechanism on the S-1 state. Several molecular motions (such as Cu-N stretching, the motion of the substituted groups etc.) with distinguishable time scales are involved in the flattening dynamics. The Fourier transformation of the time-dependent oscillation of the Cu-N bond and the N-Cu-N bond angle provides consistent conclusions with the experimental spectrum analysis. These dynamics details imply that various nuclear motions are strongly coupled in the high-dimensional excited-state potential energy surface responsible for the geometrical evolution of [Cu(dmp)(2)](+). This work provides us a unique fundamental understanding of the ultrafast photoinduced excited-state nonadiabatic process of Cu(I) complexes and their derivatives, which should have potential impacts on various research fields, such as photo-catalysts, dye-sensitized solar cells (DSSCs), and organic light emitting diodes (OLEDs).
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