Computational studies of water and carbon dioxide interactions with cellobiose.

B3LYP/6-311++G** with dispersion correction (DFT-D) was used to study local and global minimum energy structures of water (H2O) or carbon dioxide (CO2) bonding with a pair of cellobiose molecules. The calculations showed that neither the H2O nor the CO2 prefer to be between the cellobiose molecules, and that the minimum energy structures occur when these molecules bond to the outer surface of the cellobiose pair. The calculations also showed that the low energy structures have a larger number of inter-cellobiose hydrogen bonds than the high energy structures. These results indicate that penetration of H2O or CO2 between adjacent cellobiose pairs, which would assist steam or supercritical CO2 (SC-CO2) explosion of cellulose, is not energetically favored. Comparison of the energies obtained with DFT-D and DFT (the same method but without dispersion correction) show that both hydrogen bonds and van der Waals interactions play an important role in cellobiose-cellobiose interactions.