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 language | English (US) |
|---|---|
| Article number | 114303 |
| Journal | Journal of Chemical Physics |
| Volume | 151 |
| Issue number | 11 |
| DOIs | |
| State | Published - Sep 21 2019 |
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ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry
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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 journal › Article
TY - JOUR
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
AU - Castellano, Felix N.
AU - Chen, Lin X
AU - Li, Xiaosong
PY - 2019/9/21
Y1 - 2019/9/21
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85072332077&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85072332077&partnerID=8YFLogxK
U2 - 10.1063/1.5115169
DO - 10.1063/1.5115169
M3 - Article
C2 - 31542032
AN - SCOPUS:85072332077
VL - 151
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 11
M1 - 114303
ER -