Can Excited State Electronic Coherence Be Tuned via Molecular Structural Modification? A First-Principles Quantum Electronic Dynamics Study of Pyrazolate-Bridged Pt(II) Dimers

David B. Lingerfelt, Patrick J. Lestrange, Joseph J. Radler, Samantha E. Brown-Xu, Pyosang Kim, Felix N. Castellano, Lin X. Chen, Xiaosong Li*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

11 Scopus citations

Abstract

Materials and molecular systems exhibiting long-lived electronic coherence can facilitate coherent transport, opening the door to efficient charge and energy transport beyond traditional methods. Recently, signatures of a possible coherent, recurrent electronic motion were identified in femtosecond pump-probe spectroscopy experiments on a binuclear platinum complex, where a persistent periodic beating in the transient absorption signal's anisotropy was observed. In this study, we investigate the excitonic dynamics that underlie the suspected electronic coherence for a series of binuclear platinum complexes exhibiting a range of interplatinum distances. Results suggest that the long-lived coherence can only result when competitive electronic couplings are in balance. At longer Pt-Pt distances, the electronic couplings between the two halves of the binuclear system weaken, and exciton localization and recombination is favored on short time scales. For short Pt-Pt distances, electronic couplings between the states in the coherent superposition are stronger than the coupling with other excitonic states, leading to long-lived coherence. (Equation Presented).

Original languageEnglish (US)
Pages (from-to)1932-1939
Number of pages8
JournalJournal of Physical Chemistry A
Volume121
Issue number9
DOIs
StatePublished - Mar 9 2017

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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