Entropy Reorders Polariton States
Gregory D. Scholes, Courtney A. DelPo, Bryan Kudisch
Abstract
The main result is that the long-range phase coherence of the polariton states formed by strong coupling between a photon mode in a cavity and an ensemble of molecules leads to exceptionally low entropy of the upper and lower polariton states, starkly contrasting with the dark states. That result means that spectroscopy does not correctly order the free energy of the excited states because there is a significant entropic contribution to the free energy, which turns out to comparable to the electronic energy gap between the lower polariton state and the dark-state manifold. The reordered states, according to their free energy, is important to predict the potential of polariton states for reactivity, to predict spontaneous photophysical dynamics, or to understand their decoherence. The entropic contribution adds to the polariton electronic gap, rendering states surprisingly more reactive than anticipated from the input excitation energy. This apparently "additional" reactivity, evident from the thermodynamics, suggests how the low entropy of highly coherent states can be exploited as a resource.