Resolving the ultrafast intersystem crossing in a bimetallic platinum complex

Andrew J.S. Valentine, Joseph J. Radler, Alexis Mills, Pyosang Kim, Felix N. Castellano, Lin X Chen, Xiaosong Li

Research output: Contribution to journalArticle

Abstract

Bimetallic platinum complexes have interesting luminescent properties and feature long-lasting vibrational coherence and ultrafast intersystem crossing (ISC) after photoexcitation. Ultrafast triplet formation is driven by very strong spin-orbit coupling in these platinum (II) systems, where relativistic theoretical approaches beyond first-order perturbation theory are desirable. Using a fully variational relativistic theoretical method recently developed by the authors, we investigate the origins of ultrafast ISC in the [Pt(ppy) (μ-tBu2pz)]2 complex (ppy = phenylpyridine, pz = pyrazolate). Spin-orbit coupling values, evaluated along a Born-Oppenheimer molecular dynamics trajectory, are used to propagate electronic populations in time. Using this technique, we estimate ultrafast ISC rates of 15-134 fs in this species for the possible ISC pathways into the three low-lying triplet states.

Original languageEnglish (US)
Article number114303
JournalJournal of Chemical Physics
Volume151
Issue number11
DOIs
StatePublished - Sep 21 2019

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Platinum
Orbits
platinum
Photoexcitation
Molecular dynamics
Trajectories
orbits
photoexcitation
atomic energy levels
perturbation theory
trajectories
molecular dynamics
estimates
electronics

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Valentine, A. J. S., Radler, J. J., Mills, A., Kim, P., Castellano, F. N., Chen, L. X., & Li, X. (2019). Resolving the ultrafast intersystem crossing in a bimetallic platinum complex. Journal of Chemical Physics, 151(11), [114303]. https://doi.org/10.1063/1.5115169
Valentine, Andrew J.S. ; Radler, Joseph J. ; Mills, Alexis ; Kim, Pyosang ; Castellano, Felix N. ; Chen, Lin X ; Li, Xiaosong. / Resolving the ultrafast intersystem crossing in a bimetallic platinum complex. In: Journal of Chemical Physics. 2019 ; Vol. 151, No. 11.
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Resolving the ultrafast intersystem crossing in a bimetallic platinum complex. / Valentine, Andrew J.S.; Radler, Joseph J.; Mills, Alexis; Kim, Pyosang; Castellano, Felix N.; Chen, Lin X; Li, Xiaosong.

In: Journal of Chemical Physics, Vol. 151, No. 11, 114303, 21.09.2019.

Research output: Contribution to journalArticle

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T1 - Resolving the ultrafast intersystem crossing in a bimetallic platinum complex

AU - Valentine, Andrew J.S.

AU - Radler, Joseph J.

AU - Mills, Alexis

AU - Kim, Pyosang

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AU - Chen, Lin X

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