酚的 O-H 键离解的扩散蒙特卡罗研究。

A diffusion Monte Carlo study of the O-H bond dissociation of phenol.

机构信息

Kenneth S. Pitzer Center for Theoretical Chemistry, Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460, USA.

出版信息

J Phys Chem A. 2010 Sep 16;114(36):9832-5. doi: 10.1021/jp103010g.

DOI:10.1021/jp103010g

PMID:20825240

Abstract

The homolytic O-H bond dissociation energy (BDE) of phenol was determined from diffusion Monte Carlo (DMC) calculations using single determinant trial wave functions. DMC gives an O-H BDE of 87.0 +/- 0.3 kcal/mol when restricted Hartree-Fock orbitals are used and a BDE of 87.5 +/- 0.3 kcal/mol with restricted B3LYP Kohn-Sham orbitals. These results are in good agreement with the extrapolated B3P86 results of Costa Cabral and Canuto (88.3 kcal/mol), the recommended experimental value of Borges dos Santos and Martinho Simões (88.7 +/- 0.5 kcal/mol), and the G3 (88.2 kcal/mol), CBS-APNO (88.2 kcal/mol), CBS-QB3 (87.1 kcal/mol) results of Mulder.

摘要

苯酚的 O-H 键均裂解离能（BDE）是通过使用单行列式试探波函数的扩散蒙特卡罗（DMC）计算确定的。当使用限制哈特ree-fock 轨道时，DMC 给出的 O-H BDE 为 87.0 +/- 0.3 kcal/mol，而使用限制 B3LYP Kohn-Sham 轨道时，BDE 为 87.5 +/- 0.3 kcal/mol。这些结果与 Costa Cabral 和 Canuto 的扩展 B3P86 结果（88.3 kcal/mol）、Borges dos Santos 和 Martinho Simões 推荐的实验值（88.7 +/- 0.5 kcal/mol）以及 Mulder 的 G3（88.2 kcal/mol）、CBS-APNO（88.2 kcal/mol）、CBS-QB3（87.1 kcal/mol）结果非常吻合。