The intramolecular hydrogen-bond in malonaldehyde as seen by infrared spectroscopy. A four-dimensional model study
The intramolecular hydrogen-bond in malonaldehyde as seen by infrared spectroscopy. A four-dimensional model study
复制标题
DOI：
10.1524/zpch.217.12.1507.20477
复制
发表时间：
2003-01-01
影响因子：
2.5
通讯作者：
Kühn, O
中科院分区：
文献类型：
--
作者：
Doslic, N;Kühn, O
使用四维模型研究了丙二醛的 O-H-O 片段的红外光谱。这包括 OH 拉伸和两个 OH 弯曲振动以及整体 C-s 对称性假设下的 O-O 环变形模式。使用密度泛函理论计算全非简谐势能和偶极矩面，并通过迭代 Lanczos 方法求解相应的振动特征值问题。讨论了正常物质和对称氘化同位素异构体的基本和组合转变。特别强调 OH/OD 拉伸区域，它揭示了强模式混合的特征，这使得基本转换方面的简单分配变得困难。此外，还给出了热跃迁的结果，由于势能表面的拓扑结构，显示出相当不同的 OH/OD 带。采用另一种三维模型简要讨论了 H 原子隧道效应对光谱的影响，该模型考虑了面内 H 原子运动以及 O-O 距离。
The infrared spectrum of the O-H-O fragment of malonaldehyde is studied using a four-dimensional model. This comprises the OH stretching and the two OH bending vibrations as well an O-O ring deformation mode under the assumption of overall C-s symmetry. The full anharmonic potential energy and dipole moment surfaces are calculated using density functional theory and the respective vibrational eigenvalue problem is solved by an iterative Lanczos method. Fundamental and combination transitions are discussed for the normal species and the symmetrically deuterated isotopomer. Special emphasis is paid to the OH/OD stretching region which reveals the signatures of strong mode mixing what renders a simple assignment in terms of fundamental transitions difficult. In addition results for hot transitions are presented which show a rather different OH/OD band due to the topology of the potential energy surface. The influence of H atom tunneling on the spectrum is briefly addressed employing an alternative three-dimensional model which takes into account the in-plane H atom motion as well as the O-O distance.