TY - JOUR
T1 - Understanding radiative transitions and relaxation pathways in plexcitons
AU - Finkelstein-Shapiro, Daniel
AU - Mante, Pierre Adrien
AU - Sarisozen, Sema
AU - Wittenbecher, Lukas
AU - Minda, Iulia
AU - Balci, Sinan
AU - Pullerits, Tõnu
AU - Zigmantas, Donatas
PY - 2021
Y1 - 2021
N2 - Molecular aggregates on plasmonic nanoparticles have emerged as attractive systems for the studies of polaritonic light-matter states, called plexcitons. Such systems are tunable, scalable, easy to synthesize, and offer sub-wavelength confinement, all while giving access to the ultrastrong light-matter coupling regime, promising a plethora of applications. However, the complexity of these materials prevented the understanding of their excitation and relaxation phenomena. Here, we follow the relaxation pathways in plexcitons and conclude that while the metal destroys the optical coherence, the molecular aggregate coupled to surface processes significantly contributes to the energy dissipation. We use two-dimensional electronic spectroscopy with theoretical modeling to assign the different relaxation processes to either molecules or metal nanoparticle. We show that the dynamics beyond a few femtoseconds has to be considered in the language of hot electron distributions instead of the accepted lower and upper polariton branches and establish the framework for further understanding.
AB - Molecular aggregates on plasmonic nanoparticles have emerged as attractive systems for the studies of polaritonic light-matter states, called plexcitons. Such systems are tunable, scalable, easy to synthesize, and offer sub-wavelength confinement, all while giving access to the ultrastrong light-matter coupling regime, promising a plethora of applications. However, the complexity of these materials prevented the understanding of their excitation and relaxation phenomena. Here, we follow the relaxation pathways in plexcitons and conclude that while the metal destroys the optical coherence, the molecular aggregate coupled to surface processes significantly contributes to the energy dissipation. We use two-dimensional electronic spectroscopy with theoretical modeling to assign the different relaxation processes to either molecules or metal nanoparticle. We show that the dynamics beyond a few femtoseconds has to be considered in the language of hot electron distributions instead of the accepted lower and upper polariton branches and establish the framework for further understanding.
KW - cavity quantum electrodynamics
KW - excitation energy dissipation
KW - molecular aggregates
KW - open quantum systems
KW - plasmons
KW - plexcitons
KW - polaritons
KW - SDG7: Affordable and clean energy
KW - two-dimensional electronic spectroscopy
U2 - 10.1016/j.chempr.2021.02.028
DO - 10.1016/j.chempr.2021.02.028
M3 - Article
AN - SCOPUS:85104061301
SN - 2451-9308
VL - 7
SP - 1092
EP - 1107
JO - Chem
JF - Chem
IS - 4
ER -