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        "event_title":"Probing Chemistry Without Pushing It: An Electrochemical View",
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        "combined_title":"Probing Chemistry Without Pushing It: An Electrochemical View: Lior Sepunaru | UC Santa Barbara",
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        "description":"For more than a century, electrochemical kinetics have been measured largely by driving reactions away from equilibrium, most famously through Tafel analysis. This works well when a single kinetic barrier dominates, but becomes much harder to interpret when several barriers contribute or when the reaction is so fast that moving away from equilibrium immediately brings in mass transport. We recently discovered that equilibrium current fluctuations offer a way around both problems. Because the system is not being driven, the fluctuations report directly on the underlying microscopic exchange processes, allowing intrinsic kinetic information to be extracted without the usual convolution with diffusion and with the possibility of resolving more than one characteristic timescale. We are now extending this idea to adsorption and desorption at catalytic surfaces which are the elementary steps often controlling electrocatalytic reactions but are difficult to measure independently. The fluctuation magnitude and autocorrelation function provide access to both surface occupancy and characteristic adsorption\/desorption timescales. As we move into highly concentrated electrolytes, including the water-in-salt regime, we observe striking changes in these dynamics. \n\nThe second part of the talk carries the same idea into a very different environment: using electrochemistry not simply to drive a process, but to uncover the thermodynamics and kinetics hidden within it. Here, the system is a biomolecular condensate formed by liquidliquid phase separation. The classic Miller\u2013Urey experiments used electrical energy to drive chemical transformations relevant to the origins of life; in our case, we use electrical potential primarily as a probe of chemistry inside a highly concentrated biological phase. We recently found that entering a biomolecular condensate can fundamentally reshape the thermodynamic landscape of a redox reaction, an effect we probed by combining electrochemistry with OPTIR spectroscopy. One consequence is that a reaction that is nonspontaneous in ordinary aqueous solution may become spontaneous inside the condensate. We are now turning from thermodynamics to kinetics, asking whether the intrinsic rate constant itself also changes. This distinction is essential because reactions can appear much faster inside condensates simply because reactants partition strongly into the dense phase, without necessarily becoming intrinsically more reactive. More broadly, these studies ask how much of chemical reactivity is determined not only by the reacting molecules themselves, but by the microscopic environment in which the reaction occurs.",
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        "event_title":"James Davies Seminar",
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        "combined_title":"James Davies Seminar: James Davies | UC Riverside",
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