From the detailed analysis of the lowest overall barrier pathways for each product, the formation of HMF, HAA and 3FO have the lowest overall barrier of 30.98 kcal/mol, while the overall barriers for the formation of DHA and FF are slightly higher at 34.05 and 35.31 kcal/mol, respectively. Since these differences are within the accuracy of DFT, the Gibbs free energies of reaction (∆G r ) and enthalpies of reaction (∆H r ) were calculated at the Gaussian-4 level to assist the analysis of the yields of each product (Fig. ). The ∆G r , ∆H r and ∆G † max of HMF formation are the lowest among all the products, which indicates that HMF is both the kinetically and thermodynamically most favorable product. This conclusion is in agreement with the experimental observation that HMF is the predominant pyrolysis product. Although the overall barrier of HAA is the same as HMF, its ∆G r and ∆H r explain why its yield is lower, especially at low temperatures. However, considering that multiple reaction pathways can form HAA (see Fig. for more information), the yield of HAA is still predicted to be much higher than 3FO. Furthermore, the thermodynamic preference of FF formation contributes to the relatively high yield of FF, despite the sightly higher overall barrier than the other major products. To our knowledge, this represents the first reaction network that self-consistently describes the relative yields of these experimental products with complete pathways and transition states. and a double water-catalyzed ring closure with a long-distance hydrogen shift (∆G = 29.66, Fig. ), while the reaction pathway denoted as red contains a [1,5] shift (∆G = 23.33, similar to Fig. ) and a single-water-catalyzed ring closure with a shorter-distance hydrogen shift (∆G = 34.37, Fig. ). Both pathways have comparable overall and absolute barriers and predicted to be of similar kinetic relevance. Notably, the reaction mechanism represented by the combination of orange and red lines is similar to the HMF formation pathway recently proposed by Kang et al. However, the corresponding overall barrier of the reaction mechanism proposed by Kang et al. is 12 kcal/mol higher than that discovered by YARP, which discovered lower-barrier water catalyzed TSs in several steps.