Intermolecular vibrational energy transfer enabled by microcavity strong light–matter coupling

Abstract

Selective vibrational energy transfer between molecules in the liquid phase, a difficult process hampered by weak intermolecular forces, is achieved through polaritons formed by strong coupling between cavity photon modes and donor and acceptor molecules. Using pump-probe and two-dimensional infrared spectroscopy, we found that the excitation of the upper polariton, which is composed mostly of donors, can efficiently relax to the acceptors within ~5 picoseconds. The energy-transfer efficiency can be further enhanced by increasing the cavity lifetime, suggesting that the energy transfer is a polaritonic process. This vibrational energy-transfer pathway opens doors for applications in remote chemistry, sensing mechanisms, and vibrational polariton condensation.

Understanding radiative transitions and relaxation pathways in plexcitons

“…There are many interesting phenomena: delocalization, collective behavior, chemical reactivity, and remote energy transfer. [5][6][7][8][9][10][11][12][13][14][15][16][19][20][21][22][23][24][25][26][27][28] In our work, we show that we need to understand the basic excitation dynamics occurring in metals when these are strongly coupled to molecules. The stronger coupling of a plasmon to its bath than to J-aggregates means that the site states are dressed by the dissipative modes.…”

“…Cavity quantum electrodynamics (cQED) has been a very successful testbed for the quantum mechanics of light-matter interaction, [1][2][3][4] and exhibits phenomena of both fundamental and practical interest. [5][6][7][8][9][10][11][12][13][14][15][16] Dressing matter with the electromagnetic modes of a cavity results in hybrid light-matter states (polaritons) with properties that are only recently beginning to be exploited for chemistry applications, such as photocatalysis, 17,18 remote energy transfer, 11,[19][20][21][22][23][24] and polaritonic chemistry. [25][26][27][28] As the light-matter coupling strength increases, new and unexpected effects arise tied to non-zero ground-state occupation of the cavity, so that finding systems that can push the coupling into stronger regimes are desirable to explore new photophysics and photochemistry.…”

Polariton panorama

“…Organic semiconductors and molecules embedded in optical (nano)cavities under strong and ultrastrong coupling promote the dynamical formation of molecular polaritons: hybrid energy eigenstates composed of entangled photonic, electronic, and vibrational degrees of freedom [34,312,313]. Molecular polaritons were demonstrated to enhance energy transfer [314] and DC conductivity [315]. Progress with nanostructures enabled a demonstration of the strong-light matter coupling with a single molecule embedded in a plasmonic cavity [316].…”

Ultralong‐Range Polariton‐Assisted Energy Transfer in Organic Microcavities

“…[14][15][16] Vibron hybridisation effects have also been observed at room temperature, by coupling two molecular vibrational modes to the same IR electromagnetic field. [17][18][19] Other work has demonstrated hybridisation of excitons in a2 Dm aterial and an organic semiconductor,w ith the degree of hybridisation being tuneable via application of an electric field. [20] We note that excitonic hybridisation through strong coupling may enable the development of new technologies,such as an electricallyinjected, room-temperature polariton laser;here the concept of polariton condensation has been demonstrated in ahybridsemiconductor device, [21] with recent work demonstrating the electrical generation of organic-exciton polaritons in ac oupled-cavity device containing as eries of inorganic quantum wells.…”