Vishnu Chari @Vishnu-Chari

I encountered the calculations in the research article titled "Article Theoretical studies on electrochemistry of p-aminophenol

." However, I'm having difficulty comprehending the procedure used to calculate ΔrG20 and ΔrG30, particularly when incorporating solvent model adjustments. My confusion lies in the precise method for calculating the correction terms when considering the solvent model. I've included the worksheet I employed in an attempt to replicate the results showcased in Table 3 of the mentioned article.

In Table 3 of the paper, it is stated that ΔrG20 equals −44.433 kJ/mol. Strikingly, my calculations yield a value of -26.707 kJ/mol for ΔrG20. Furthermore, for ΔrG30, the paper indicates a value of −28.424 kJ/mol, whereas my calculations result inΔrG30 = -23.355 kJ/mol. Regarding the computed redox potential (E0) using the B3LYP/6-31G(d,p) level of theory, the article reports a value of 0.682 V, but my calculations yield 0.616 V.

I would be extremely grateful for any guidance or assistance you could provide in resolving these discrepancies or any other methods (not the use of isodesmic reactions) to calculate the redox potentials of aforementioned systems using DFT calculations.