title: Modified relaxation dynamics and coherent energy exchange in coupled vibration-cavity polaritons.
abstract: Coupling vibrational transitions to resonant optical modes creates vibrational polaritons shifted from the uncoupled molecular resonances and provides a convenient way to modify the energetics of molecular vibrations. This approach is a viable method to explore controlling chemical reactivity. In this work, we report pump-probe infrared spectroscopy of the cavity-coupled C-O stretching band of W(CO)6and the direct measurement of the lifetime of a vibration-cavity polariton. The upper polariton relaxes 10 times more quickly than the uncoupled vibrational mode. Tuning the polariton energy changes the polariton transient spectra and relaxation times. We also observe quantum beats, so-called vacuum Rabi oscillations, between the upper and lower vibration-cavity polaritons. In addition to establishing that coupling to an optical cavity modifies the energy-transfer dynamics of the coupled molecules, this work points out the possibility of systematic and predictive modification of the excited-state kinetics of vibration-cavity polariton systems.
authors.affiliation: National Research Council Postdoctoral Associate, Chemistry Division, U. S. Naval Research Laboratory, Washington, District of Columbia 20375, USA.
authors.forename: A D
authors.initials: AD
authors.lastname: Dunkelberger
authors.affiliation: National Research Council Postdoctoral Associate, Chemistry Division, U. S. Naval Research Laboratory, Washington, District of Columbia 20375, USA.
authors.forename: B T
authors.initials: BT
authors.lastname: Spann
authors.affiliation: Chemistry Division, Naval Research Laboratory, Washington, District Of Columbia 20375, USA.
authors.forename: K P
authors.initials: KP
authors.lastname: Fears
authors.affiliation: Chemistry Division, Naval Research Laboratory, Washington, District Of Columbia 20375, USA.
authors.forename: B S
authors.initials: BS
authors.lastname: Simpkins
authors.affiliation: Chemistry Division, Naval Research Laboratory, Washington, District Of Columbia 20375, USA.
authors.forename: J C
authors.initials: JC
authors.lastname: Owrutsky