论文部分内容阅读
在B3LYP/6-311++G**[I-离子使用赝势基组(4s4pld)/(2s2pld)]水平下得到X-.H2O(X=F,Cl,Br,I)复合物优化构型。经MP2校正电子相关能及基组叠加误差(BSSE)在相同基组下单点校正,求得精确的单体间相互作用能的大小。由自然键轨道(NBO)分析揭示了相互作用的本质,阐述了相互作用的强度以及它对复合物构型和振动参数的影响。经分析得到电荷由X-离子的孤对电子迁移(CT)到σ*OH(…X)反键上,σ*OH(…X)的自然布居数增加,削弱了σOH(…X)键使σOH(…X)键增长,力常数变小,导致红移(与单体H2O相比),与实验值非常吻合,且它们之间具有很好的相关性,同时,红移强度加强。
The optimized structure of X-H 2 O (X = F, Cl, Br, I) complexes at B3LYP / 6-311 ++ G ** [I- ions using the pseudopotential group (4s4pld) / (2s2pld) type. After the MP2 correction electron correlation energy and the base-group superposition error (BSSE) are corrected single-point under the same basis set, the exact inter-monomer interaction energy can be obtained. The analysis of the natural bond orbital (NBO) reveals the nature of the interaction and illustrates the strength of the interaction and its effect on the configuration and vibration parameters of the composite. It has been found that the natural population of σ * OH (... X) increases with the increase of the soliton from the lone pair electron transfer (CT) of the X-ion to the σ * OH (... X) With the increase of σOH (X) bond, the force constant becomes smaller, leading to redshift (compared with monomer H2O), which is in good agreement with the experimental data and has a good correlation between them. At the same time, the redshift intensity is strengthened.