G3B3和CBS-QB3在化学键裂解能计算中的相关研究

The performance of the newly developed G3B3 and CBS-QB3 methods in calculating absolute bond dissociation energy (BDE) was assessed. It was found that these two methods could predict the BDE with an accuracy of about 8.4 kJ/mol and therefore, they exlfibited similar performance as the standard G3 and CBS-Q methods. On the other hand, it was demonstrated that the B3LYP method significantly underestimated the absolute BDE by 16.7—20.9 kJ/mol. This finding was valuable and timely because many researchers could use this relatively cheap method in studying radical reactions. Finally, 38 compounds were showed for which the theoretical BDE seriously deviated from the experimental data.     

Influence of a Hydrophobic Environment on the Structure of Arginine—Carboxylate Salt Bridge

The exact structure of an arginine-carboxylate salt bridge in different chemical environments remains a controversial problem.In the present work,the zwitterionic and neutral forms of arginine-carboxylate salt bridge were studied by the B3LYP/6-311G(d,p)//PM3 method.It turns out that the neutral forms are more stable than the zwitterionic coumterparts in gas phase.However,whnen bound by α-cyclodextrin,the zwitterionic forms become more stable than the corresponding neutral ones.It is suggested that the hydrophobic environment provided by the cyclodextrin cavity leads to such behavior.Therefore,the salt bridge still could be in a zwitterionic form in the hydrophobic interior of the real proteins.