Arrhenius-law-governed homo- and heteroduplex dissociation

A simple model of temperature-increase-driven homo- or heteroduplex dissociation is analyzed. It features a temperature-independent association constant, and a dissociation constant that increases with temperature according to an Arrhenius law. The model is analytically tractable for quasiequilibrium conditions, for two special cases in the intermediate regime, and in the strongly irreversible regime. In the latter, the fraction of isolated components depends on temperature according to a Gumbel minimal value distribution. The model suggests a logarithmic dependence of the dissociation temperature on the rate of temperature increase. It further predicts that the dissociation occurs in a twice broader temperature interval for slow than fast temperature increase. Finally, the model points to a previously overlooked source of discrepancy between apparent van't Hoff and calorimetric enthalpies. Applied to short double stranded DNA, the model explains the dependence of the melting temperature on the rate of temperature increase, and the twice lower width of the melting transition in low salt compared to high salt conditions.