胺基自由基绝热电离能的理论计算研究-陕西师范大学学报期刊社网站

陕西师范大学学报（自然科学版）

化学与材料科学

胺基自由基绝热电离能的理论计算研究

田巍1,姚建永2,王渭娜1,王文亮1*

(1 陕西师范大学化学与材料科学学院, 陕西西安 710062； 2 山东新华制药股份有限公司, 山东淄博 255005)

田巍, 男, 硕士研究生, 主要从事化学反应动力学的理论研究.

摘要:

采用密度泛函理论 B3LYP、BB1K、MPW1K、MPWB1K、MPW1B95和耦合簇理论CCSD(T)方法, 分别用6-31+G(d,p)、6-311+G(d,p)、6-311++G(2d,2p)、6-311++G(2df,2p)、6-311G(3df,3pd)和6-311++G(3df,3pd) 6种基组对胺基自由基的绝热电离能进行了理论计算. 研究表明,零点能校正和弥散基函数引入可以明显改善电离能计算结果, MPW1B95/6-311++G(3df,3pd) 给出与实验非常相近的结果. MPWB1K 计算结果普遍严重偏离实验值, 不适合胺基自由基电离能的计算.

关键词：

胺基自由基；绝热电离能；密度泛函理论；耦合簇方法CCSD(T)

收稿日期：

2008-03-16

中图分类号：

O641.121

文献标识码：

文章编号：

1672-4291(2009)02-0060-04

基金项目：

陕西省自然科学基金资助项目(2006B12)

Doi:

Theoretical calculations on the adiabatic ionization energy of amidogen radical

TIAN Wei1, YAO Jian-yong2, WANG Wei-na1, WANG Wen-liang1*

(1 College of Chemistry and Materials Science, Shaanxi Normal University, Xi′an 710062, Shaanxi, China; 2 Shandong Xinhua Pharmaceutical Limited Company, Zibo 255005, Shandong, China)

Abstract:

The theoretical calculations of the adiabatic ionization energy(AIE) of amidogen radical have been carried out at the B3LYP, BB1K, MPW1K, MPWB1K, MPW1B95 and CCSD(T) levels of thoery with the 6-31+G(d,p), 6-311+G(d,p), 6-311++G(2d,2p), 6-311++G(2df,2p), 6-311G(3df,3pd), and 6-311++G(3df,3pd) basis sets. The calculated results show that the accuracy of the AIE is obviously improved by the zero-point energy correction and increasing diffuse functions. The calculated AIE by the MPW1B95/6-311++G(3df,3pd) method accords much better with the experimental value than that by the other methods. The MPWB1K method is not suitable for calculating AIE of amidogen radical due to the considerable deviation (3.73eV) from the experimental value. Basd on the present study, we expect that the MPW1B95/6-311++G(3df,3pd) method can be extended to calculate the AIE of the class of amines.

KeyWords:

amidogen radical; adiabatic ionization energy; density functional theory (DFT); coupled cluster method CCSD(T)