Molecular isomerization fundamentally involves quantum states bound within a potential energy function with multiple minima. For isolated gas-phase molecules, eigenstates well above the isomerization saddle points have been characterized. However, to observe the quantum nature of isomerization, systems in which transitions between the eigenstates occur—such as condensed-phase systems—must be studied. Efforts to resolve quantum states with spectroscopic tools are typically unsuccessful for such systems. An exception is CO adsorbed on NaCl(100), which is bound with the well-known OC–Na+ structure. We observe an unexpected upside-down isomer (CO–Na+) produced by infrared laser excitation and obtain well-resolved infrared fluorescence spectra from highly energetic vibrational states of both orientational isomers. This distinctive condensed-phase system is ideally suited to spectroscopic investigations of the quantum nature of isomerization.
Using a mid-infrared emission spectrometer based on a superconducting nanowire single-photon detector, we observed the dynamics of vibrational energy pooling of carbon monoxide (CO) adsorbed at the surface of a sodium chloride (NaCl) crystal. After exciting a majority of the CO molecules to their first vibrationally excited state (v = 1), we observed infrared emission from states up to v = 27. Kinetic Monte Carlo simulations showed that vibrational energy collects in a few CO molecules at the expense of those up to eight lattice sites away by selective excitation of NaCl’s transverse phonons. The vibrating CO molecules behave like classical oscillating dipoles, losing their energy to NaCl lattice vibrations via the electromagnetic near-field. This is analogous to Sommerfeld’s description of radio transmission along Earth’s surface by ground waves.
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