苯酚、水及苯酚 - 水团簇中的氢键作用

Hydrogen bonding in phenol, water, and phenol-water clusters.

作者信息

Parthasarathi R, Subramanian V, Sathyamurthy N

机构信息

Chemical Laboratory, Central Leather Research Institute, Adyar, Chennai, India.

出版信息

J Phys Chem A. 2005 Feb 10;109(5):843-50. doi: 10.1021/jp046499r.

DOI:10.1021/jp046499r

PMID:16838955

Abstract

Structure, stability, and hydrogen-bonding interaction in phenol, water, and phenol-water clusters have been investigated using ab initio and density functional theoretical (DFT) methods and using various topological features of electron density. Calculated interaction energies at MP2/6-31G level for clusters with similar hydrogen-bonding pattern reveal that intermolecular interaction in phenol clusters is slightly stronger than in water clusters. However, fusion of phenol and water clusters leads to stability that is akin to that of H(2)O clusters. The presence of hydrogen bond critical points (HBCP) and the values of rho(r(c)) and nabla(2)rho(r(c)) at the HBCPs provide an insight into the nature of closed shell interaction in hydrogen-bonded clusters. It is shown that the calculated values of total rho(r(c)) and nabla(2)rho(r(c)) of all the clusters vary linearly with the interaction energy.

摘要

利用从头算和密度泛函理论（DFT）方法，并借助电子密度的各种拓扑特征，对苯酚、水以及苯酚 - 水团簇中的结构、稳定性和氢键相互作用进行了研究。在MP2/6 - 31G水平下，对具有相似氢键模式的团簇计算得到的相互作用能表明，苯酚团簇中的分子间相互作用略强于水团簇。然而，苯酚和水团簇的融合导致了类似于H₂O团簇的稳定性。氢键临界点（HBCP）的存在以及HBCP处的ρ(rₑ)和∇²ρ(rₑ)值，为洞察氢键团簇中闭壳层相互作用的本质提供了依据。结果表明，所有团簇的总ρ(rₑ)和∇²ρ(rₑ)计算值与相互作用能呈线性变化。