A ROTATIONAL HAMILTONIAN FOR THE GROUND VIBRATIONAL STATE OF HYDRAZINE
A ROTATIONAL HAMILTONIAN FOR THE GROUND VIBRATIONAL STATE OF HYDRAZINE
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肼基振动态的旋转哈密顿量
DOI：
10.1016/0022-2852(81)90025-4
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发表时间：
1981
影响因子：
1.4
通讯作者：
J. T. Hougen
中科院分区：
文献类型：
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作者：
J. T. Hougen
得到了适合于肼分子基态振动和电子态转动能级拟合的哈密顿矩阵。该矩阵的维度为16 × 16，其中标记行和列的16个函数由近长轴不对称转子偶极子的两个成员组成（给定|Ka|）的八种不同的，但化学上等价的，构象分子可以达到的各种组合的-NH 2在分子的任何一端的反转，和内部旋转的N N键。该矩阵是在一个唯象的方式，通过应用组理论参数的模型，其中隧道之间的各种框架被假定为非常缓慢的振动频率相比。大振幅振动势面和相关的隧道路径的综合治疗尚未进行，也没有四次（J 4）离心畸变效应被认为是在一个系统的方式。初步拟合表明，开发的模型可以用来拟合联氨微波数据在一个一致的方式，并充分处理这些数据已经进行。
A Hamiltonian matrix suitable for fitting rotational energy levels of the hydrazine molecule in its ground vibrational and electronic states was obtained. This matrix is of dimension 16 × 16, where the 16 functions labeling the rows and columns consist of the two members of a near-prolate asymmetric rotor doublet (with given |Ka|) for the eight different, but chemically equivalent, conformers which the molecule can reach by various combinations of -NH2inversion at either end of the molecule, and internal rotation about the NN bond. The matrix is derived in a phenomenological fashion, by applying group theoretical arguments to a model in which tunneling among the various frameworks is assumed to be very slow compared with the vibrational frequencies. A comprehensive treatment of the large-amplitude vibrational potential surfaces and associated tunneling pathways has not been carried out, nor have quartic (J4) centrifugal distortion effects been considered in a systematic fashion. Preliminary fits indicate that the model developed can be used to fit the hydrazine microwave data in a consistent fashion, and a full treatment of such data has been undertaken.