Anomalous (Exergonic) Behavior in the Transfer of Electrons between Donors and Acceptors: Mobility, Energy, Caloric Capacity, and Entropy

Abstract

Understanding the kinetics of electron transfer reactions involves active research in physics, chemistry, biology, and nano-tech. Here, we propose a model to apply in a broader framework by establishing a connection between thermodynamics and kinetics. From a purely thermodynamic point of view, electronic transfer Marcus’ theory is revisited; consequently, calculations of thermodynamic variables such as mobility, energy, and entropy are provided. More significantly, two different regimes are explicitly established. In the anomalous region, an exergonic process associated with negative heat capacity appears. Further, in the same region, mobility, energy, and entropy decrease when the temperature increases.

Computational prediction of the properties of bis(ethynylthienyl)dialcoxynaphthalene‐based conjugated polymers for organic solar cell applications

“…At room temperature, the charge carrier transport in π-conjugated materials can be described as a sequential charge carrier hopping between neighboring segments [30,33,48]. The ate of the charge-transfer process (k CT ) can be calculated by the Marcus semiclassical theory (Equation 9).…”

“…Density functional theory (DFT) is a powerful chemical computational tool that has demonstrated accuracy in screening new materials and predicting their optoelectronic properties at reasonable computational costs while saving time and bench workload [30]. In addition, Scharber's model [31] and Marcus semiclassical theory [32,33] were used to evaluate the potential of the 1,4-NET-based CPs in PSC applications, compared to previously reported EHONDT-based polymer P6.…”