Information theory for analyzing heterogeneous electron transfer dynamics under steady-state conditions

Information entropy production for steady-state electrochemical systems

“…In the present paper, we extend our previous works in which we have introduced a probabilistic approach for analyzing the dynamics of an electrochemical system under steady-state conditions [12,13]. Here, we combine non-equilibrium thermodynamic and information theory formalisms to provide a theoretical basis for the determination of the information entropy production.…”

“…Furthermore, we have reported that the distribution function P(n ox , e) can be determined by using the principle of maximum entropy [13]. As a result, a Gaussian distribution function that approximated well P(n ox , e) was obtained.…”

“…Also, the mass transport is governed by the diffusion. In our previous work [12,13], we have introduced a dimensionless variable n Ox (with 0 6 n Ox 6 1) that allows calculating the degree of advancement for the above redox reaction as:…”

“…For a steady-state electrochemical system, we have previously introduce a distribution function P(n Ox , e) defined as [12,13] Pðn Ox ; eÞ ¼…”

“…These functions allowed us to quantify the departure from the reversible behaviour. In particular, we showed that the cross-entropy can be used to determine the electrochemical features of the electrochemical system under consideration, such as the standard heterogeneous rate constant [13].…”