Bond dissociation energies for removal of the hydroxyl group in some alcohols from quantum chemical calculations

作者：Zhao, Jun^*; Zeng, Hui; Cheng, Xinlu

来源：International Journal of Quantum Chemistry, 2012, 112(3): 665-671.

DOI：10.1002/qua.23037

• density functional theory
• bond dissociation energy
• CBS-Q method
• equilibrium structure
• alcohols

In this theoretical work, 22 alcohols and their geometric structure properties have been investigated employing quantum chemical methods to calculate the C?OH equilibrium bond distances and bond dissociation energies (BDEs). Since DFT methods have been researched to have low basis sets sensitivity for small and medium molecules in our previous work (Zhao et al., J Mol Struct, 2006, 766, 87), 22 title compounds have been studied by employing the hybrid density functional theory (B3LYP, B3PW91, B3P86, PBE1PBE) in conjunction with the 6-311G** basis set and the complete basis set (CBSQ) method. Comparison with the available experimental data shows that CBSQ and B3P86 methods calculated results agree very well with the experimental values, with the average absolute errors of 1.3 kcal/mol and 3.5 kcal/mol, respectively. So considering the expensive computational time, CBSQ method can be chosen as a satisfactory method of predicting the accurate BDEs for removal of the OH group in small and medium size alcohols. And B3P86 method may give accurate BDEs for larger alcohols we haven't studied.

• 出版日期2012-2-5
• 单位四川大学; 长江大学