@article{3b8a78652a0847e2820599c28df64edf,
title = "Resolving the ultrafast intersystem crossing in a bimetallic platinum complex",
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.",
author = "Valentine, {Andrew J.S.} and Radler, {Joseph J.} and Alexis Mills and Pyosang Kim and Castellano, {Felix N.} and Chen, {Lin X.} and Xiaosong Li",
note = "Funding Information: The development of the two-component electronic structure method was funded by the U.S. Department of Energy (Grant No. DE-SC0006863). The development of nonperturbative spectroscopic methods was supported by the National Science Foundation (Grant No. CHE-1856210). Funding for the synthesis (Grant No. CHE-1665033) and spectroscopic analysis (Grant No. CHE-1665021) of platinum dimer complexes was provided by the National Science Foundation. Computational intersystem crossing was partially supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences, through the Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Computations were facilitated through the use of advanced computational, storage, and networking infrastructure provided by the Hyak supercomputer system at the University of Washington, funded by the Student Technology Fee and the National Science Foundation (Grant No. MRI-1624430). Publisher Copyright: {\textcopyright} 2019 Author(s).",
year = "2019",
month = sep,
day = "21",
doi = "10.1063/1.5115169",
language = "English (US)",
volume = "151",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "11",
}