物理化学学报 >> 2012, Vol. 28 >> Issue (02): 315-323.doi: 10.3866/PKU.WHXB201111232

理论与计算化学 上一篇    下一篇

分子筛限域孔道中吡啶的吸附结构和能量

韩冰1,2, 褚月英1,2, 郑安民1, 邓风1   

  1. 1. 中国科学院武汉物理与数学研究所, 波谱与原子分子物理国家重点实验室, 武汉核磁共振中心, 武汉 430071;
    2. 中国科学院研究生院, 北京 100049
  • 收稿日期:2011-10-09 修回日期:2011-11-17 发布日期:2012-01-11
  • 通讯作者: 郑安民, 邓风 E-mail:zhenganm@wipm.ac.cn; dengf@wipm.ac.cn
  • 基金资助:

    国家自然科学基金(21073228, 20933009, 20921004)及国家重点基础研究发展规划项目(973) (2009CB918600)资助

Adsorption Structure and Energy of Pyridine Confined inside Zeolite Pores

HAN Bing1,2, CHU Yue-Ying1,2, ZHENG An-Min1, DENG Feng1   

  1. 1. Wuhan Center for Magnetic Resonance, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, P. R. China;
    2. Graduate University of Chinese Academy of Sciences, Beijing 100049, P. R. China
  • Received:2011-10-09 Revised:2011-11-17 Published:2012-01-11
  • Contact: ZHENG An-Min, DENG Feng E-mail:zhenganm@wipm.ac.cn; dengf@wipm.ac.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21073228, 20933009, 20921004) and National Key Basic Research Program of China (973) (2009CB918600).

摘要: 以吸附于ZSM-5孔道中的吡啶分子为例, 利用量子化学理论方法考察了计算模型和密度泛函方法的选择对吡啶吸附结构和吸附能的影响, 从而为准确计算分子筛限域孔道中客体分子吸附态结构和能量参数提供了依据. 计算结果表明, 吡啶吸附能随着所选用的分子筛的计算模型(从8T到128T)增大而增大, 当选用的孔道结构能够将整个分子筛的孔道结构完全包括进来的时候(72T)达到收敛. 与常规的密度泛函方法(B3LYP 和M06-2X)相比较, 考虑到色散作用校正的B97D泛函方法能够很好地处理分子筛体系中主客体间的长程相互作用和弱相互作用, 计算得到的能量数据与实验结果符合得很好.

关键词: 量子化学计算, 分子筛, 限域效应, 吸附能

Abstract: The performance of different exchange-correlation functionals for the description of the interaction of pyridine with different cluster models of ZSM-5 zeolite has been assessed. Theoretical calculations show that upon increasing the cluster model from 8T to 128T, the adsorption energy of pyridine in ZSM-5 zeolite increases gradually and reaches convergence by the 72T cluster model. On the basis of the 72T cluster model, the pyridine adsorption energy calculated with different functionals is further examined. Compared to the conventional functionals (B3LYP and M06-2X), the B97D functional which takes into account the dispersion correction provides calculated results that agree well with experimental data. The present results indicate that the B97D functional is suitable for studying long-range interactions in weakly interacting systems.

Key words: Quantum chemical calculation, Zeolite, Confinement effect, Adsorption energy

MSC2000: 

  • O641