Role of Vibrational Dynamics on Excited-State Electronic Coherence in a Binuclear Platinum Complex
[2];
[3];
[1]
- Department of Chemistry, University of Washington, Seattle, Washington 98195, United States
- Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, United States
- Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States
Long-lived quantum coherence between excited electronic states can enable highly efficient energy and charge transport processes in chemical systems. Recent pump-probe experiments on binuclear platinum complexes identified persistent, periodic beating of transient absorption anisotropy signals, indicating long excited-state coherence lifetimes. Our previous simulations of the electronic dynamics of these complexes indicate that coherence lifetimes are sensitive to the balance between competitive electronic couplings. The complexes with shorter Pt-Pt distances underwent no appreciable dephasing in the limit of static nuclei, motivating the inclusion of nuclear motion into our simulations. The tert-butyl-substituted complex is studied in this work using the Ehrenfest method for mixed quantum classical dynamics to investigate the role of vibrational dynamics on a complex shown to support coherence lifetimes. Results indicate that the inclusion of excited-state vibrations drives a rapid collapse of the two-state coherence prior to the experimentally determined intersystem crossing. This further suggests singlet excited-state coherences may not be prerequisites for long-lived triplet coherences.
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- DOE Contract Number:
- AC02-06CH11357
- OSTI ID:
- 1473676
- Journal Information:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 122, Issue 23; ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
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