Ultrafast vibrational excitation transfer on resonant antenna lattices revealed by two-dimensional infrared spectroscopy

High-quality lattice resonances in arrays of infrared antennas operating in an open-cavity regime form polariton states by means of strong coupling to molecular vibrations. We studied polaritons formed by carbonyl stretching modes of (poly)methyl methacrylate on resonant antenna arrays using femtosecond 2DIR spectroscopy. At a normal incidence of excitation light, doubly degenerate antenna-lattice resonances (ALRs) form two polariton states: a lower polariton and an upper polariton. At an off-normal incidence geometry of 2DIR experiments, the ALR degeneracy is lifted and, consequently, the polariton energies are split. We spectrally resolved and tracked the time-dependent evolution of a cross-peak signal associated with the excitation of reservoir states and the unidirectional transfer of the excess energy to lower polaritons. Bi-exponential decay of the cross-peak suggests that a reversible energy exchange between the bright and dark lower polaritons occurs with a characteristic transfer time of ∼200 fs. The cross-peak signal further decays within ∼800 fs, which is consistent with the relaxation time of the carbonyl stretching vibration and with the dephasing time of the ALR. An increase in the excitation pulse intensity leads to saturation of the cross-peak amplitude and a modification of the relaxation dynamics. Using quantum-mechanical modeling, we found that the kinetic scheme that captures all the experimental observations implies that only the bright lower polariton accepts the energy from the reservoir, suggesting that transfer occurs via a mechanism involving dipole-dipole interaction. An efficient reservoir-to-polariton transfer can play an important role in developing novel room-temperature quantum optical devices in the mid-infrared wavelength region.