H_2O与NO,CN,OH自由基及负离子相互作用的CP研究  

Study of Intermolecular Interaction between H_2O and NO, CN, OH Radicals and Anions

作　　者：郑文旭[1] 蒲雪梅[1] 王伟周[1] 田安民[1] 

机构地区：[1]四川大学化学学院,成都610064

出　　处：《化学学报》2003年第3期336-344,共9页Acta Chimica Sinica

基　　金：香港城市大学StrategicGrand (No .70 0 0 939)资助项目

摘　　要：采用量子化学从头算方法在均衡 (Counterpoise)校正和非校正势能面上研究了H2 O与NO ,NO-,CN ,CN-,OH ,OH-之间的相互作用 .比较了CP 梯度优化和非校正梯度优化以及基组的选择对超分子结构和能量的影响 .研究表明 ,6 311++g 基组对于这些体系的研究有很高的效率 .这些自由基和负离子均能与H2 O形成强弱不同的氢键 .按相互作用的强弱次序依次为OH-,CN-,NO-,OH ,CN ,NO ,由相互作用能ΔECP,成键临界点电荷密度 ρ ,二阶稳定化相互作用能E( 2 )分析均得到同样结果 .CPGeometry optimizations are carried out for the CN-H2O, CN- -H2O, NO-H2O, NO- -H2O, HO-H2O, and OH- -H2O intermolecular complexes on both the uncorrected and U-corrected potential energy hypersurfaces. Because of the correction of the BSSE during the gradient optimization, CP-corrected gradient optimization is more prior than normal optimization in structure research. But there is no significant difference between CP-corrected gradient optimization and normal optimization at interaction energies and BSSE. The diffusive basis functions are necessary for all the present systems. 6-311 ++ g** basis set is efficient to these systems for its good results with low time consumption. These radicals and anions all can form hydrogen bonding with H2O. In the order of OH-, CN-, NO-, OH, CN, NO, the interaction force changes from strong to weak. The same results can be obtained by analysis of interaction energy DeltaE, the electron density rho of critical points, and the stabilization interaction energies E(2).

关 键 词：分子间相互作用 CP-梯度优化 基函数迭加误差 氰基自由基 量子化学 从头算 水 氮氧自由基 羟基自由基 溶剂 

分 类 号：O641[理学—物理化学]