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 journalArticle

4 Citations (Scopus)

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

Fingerprint

Quantum electronics
quantum electronics
Excited states
Dimers
dimers
Platinum
electronics
excitation
platinum
Anisotropy
Pumps
Spectroscopy
excitons
signatures
pumps
anisotropy
probes
Experiments
spectroscopy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Lingerfelt, David B. ; Lestrange, Patrick J. ; Radler, Joseph J. ; Brown-Xu, Samantha E. ; Kim, Pyosang ; Castellano, Felix N. ; Chen, Lin X ; Li, Xiaosong. / Can Excited State Electronic Coherence Be Tuned via Molecular Structural Modification? A First-Principles Quantum Electronic Dynamics Study of Pyrazolate-Bridged Pt(II) Dimers. In: Journal of Physical Chemistry A. 2017 ; Vol. 121, No. 9. pp. 1932-1939.
@article{e1690083ab6f463eb6aee8365e02fa2e,
title = "Can Excited State Electronic Coherence Be Tuned via Molecular Structural Modification? A First-Principles Quantum Electronic Dynamics Study of Pyrazolate-Bridged Pt(II) Dimers",
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).",
author = "Lingerfelt, {David B.} and Lestrange, {Patrick J.} and Radler, {Joseph J.} and Brown-Xu, {Samantha E.} and Pyosang Kim and Castellano, {Felix N.} and Chen, {Lin X} and Xiaosong Li",
year = "2017",
month = "3",
day = "9",
doi = "10.1021/acs.jpca.6b12099",
language = "English (US)",
volume = "121",
pages = "1932--1939",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "9",

}

Can Excited State Electronic Coherence Be Tuned via Molecular Structural Modification? A First-Principles Quantum Electronic Dynamics Study of Pyrazolate-Bridged Pt(II) Dimers. / Lingerfelt, David B.; Lestrange, Patrick J.; Radler, Joseph J.; Brown-Xu, Samantha E.; Kim, Pyosang; Castellano, Felix N.; Chen, Lin X; Li, Xiaosong.

In: Journal of Physical Chemistry A, Vol. 121, No. 9, 09.03.2017, p. 1932-1939.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Can Excited State Electronic Coherence Be Tuned via Molecular Structural Modification? A First-Principles Quantum Electronic Dynamics Study of Pyrazolate-Bridged Pt(II) Dimers

AU - Lingerfelt, David B.

AU - Lestrange, Patrick J.

AU - Radler, Joseph J.

AU - Brown-Xu, Samantha E.

AU - Kim, Pyosang

AU - Castellano, Felix N.

AU - Chen, Lin X

AU - Li, Xiaosong

PY - 2017/3/9

Y1 - 2017/3/9

N2 - 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).

AB - 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).

UR - http://www.scopus.com/inward/record.url?scp=85015831517&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85015831517&partnerID=8YFLogxK

U2 - 10.1021/acs.jpca.6b12099

DO - 10.1021/acs.jpca.6b12099

M3 - Article

VL - 121

SP - 1932

EP - 1939

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 9

ER -