The validity of the hard-sphere model in hydrogen bonded intermolecular interactions of HCN–HF
The validity of the hard-sphere model in hydrogen bonded intermolecular interactions of HCN–HF
复制标题
HCN-HF 氢键分子间相互作用硬球模型的有效性
DOI：
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发表时间：
1997
期刊：
影响因子：
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通讯作者：
J. Bevan
中科院分区：
文献类型：
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作者：
A. McIntosh;A. M. Gallegos;R. Lucchese;J. Bevan
最近获得的HCN-HF激发振动态的光谱常数，在ν7分子间弯曲模式中具有多达5个量子，其特征在于主要是HCN受阻旋转，和ν4分子间伸缩模中的一个量子与该体系的早期实验数据相结合，得到了一个约化的分子间势能面，其中HF碎片被视为假原子，HCN被视为假原子。碎片被视为刚性转子。假设相互作用势为泛函形式，用振动组态相互作用方法研究了振动动力学。改变电位中的参数以获得与所有可用实验数据的最佳拟合。由此产生的相互作用势被发现在ν4和ν7振动模式之间具有强耦合。约束最小值在该表面上的轨迹与Buckingham-Fowler模型中使用的硬球假设非常一致[A. D.白金汉
Recently obtained spectroscopic constants for excited vibrational states of HCN–HF with up to five quanta in the ν7 intermolecular bending mode, which can be characterized as being mostly HCN hindered rotation, and one quanta in the ν4 intermolecular stretching mode were combined with earlier experimental data on this system to obtain a reduced intermolecular potential energy surface where the HF fragment was treated as a pseudoatom and the HCN fragment was treated as a rigid rotor. A functional form was assumed for the interaction potential and the vibrational dynamics was studied using a vibrational configuration interaction method. The parameters in the potential were varied to obtain the best fit to all available experimental data. The resulting interaction potential was found to have a strong coupling between the ν4 and ν7 vibrational modes. The locus of constrained minima on this surface was in excellent agreement with the hard-sphere assumption used in the Buckingham–Fowler model [A. D. Buckingham ...