RESUMEN
Single molecules are nanoscale thermodynamic systems with few degrees of freedom. Thus, the knowledge of their entropy can reveal the presence of microscopic electron transfer dynamics that are difficult to observe otherwise. Here, we apply thermocurrent spectroscopy to directly measure the entropy of a single free radical molecule in a magnetic field. Our results allow us to uncover the presence of a singlet to triplet transition in one of the redox states of the molecule, not detected by conventional charge transport measurements. This highlights the power of thermoelectric measurements which can be used to determine the difference in configurational entropy between the redox states of a nanoscale system involved in conductance without any prior assumptions about its structure or microscopic dynamics.
Asunto(s)
Entropía , Transporte de Electrón , Análisis Espectral , TermodinámicaRESUMEN
The entropy of a system gives a powerful insight into its microscopic degrees of freedom; however, standard experimental ways of measuring entropy through heat capacity are hard to apply to nanoscale systems, as they require the measurement of increasingly small amounts of heat. Two alternative entropy measurement methods have been recently proposed for nanodevices: through charge balance measurements and transport properties. We describe a self-consistent thermodynamic framework for applying thermodynamic relations to few-electron nanodevices-small systems, where fluctuations in particle number are significant, whilst highlighting several ongoing misconceptions. We derive a relation (a consequence of a Maxwell relation for small systems), which describes both existing entropy measurement methods as special cases, while also allowing the experimentalist to probe the intermediate regime between them. Finally, we independently prove the applicability of our framework in systems with complex microscopic dynamics-those with many excited states of various degeneracies-from microscopic considerations.