Computer assistance in the analysis of molecular spectra: I. Rotational structure of high resolution singlet-singlet bands
Computer assistance in the analysis of molecular spectra: I. Rotational structure of high resolution singlet-singlet bands
复制标题
分子光谱分析中的计算机辅助：一、高分辨率单重态-单重态带的旋转结构
DOI：
10.1016/0010-4655(85)90048-7
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发表时间：
1985
影响因子：
6.3
通讯作者：
D. A. Ramsay
中科院分区：
文献类型：
--
作者：
F. W. Birss;D. A. Ramsay
非线性分子的振动带和振动带的转动结构的分析提出了两类需要计算机辅助解决的问题。一个是涉及的数据量。经常会遇到这样的例子，其中可以分配超过1000个已解析行。另一个问题是过渡中涉及的两个状态的模型哈密顿量的复杂性。由于这些光谱中经常涉及相对较高的j和K值，因此哈密顿量必须包括六次方离心畸变项，以便获得光学精度（2 0.001 cm- '）的实验数据的适当表示。此外，计算特征值和特征函数的方法涉及在对称转子函数的基础上对角化哈密顿量的矩阵表示。通常，这涉及100个维度从1到25的矩阵。最初的程序包含了对哈密顿函数参数进行最小二乘改进所需的最小值，但随着它的使用越来越频繁，人们意识到它可以变成一个“黑盒子”，光谱学家可以使用它，而不需要对编程和计算机管理能力提出过多的要求。我们在本文中描述的正是这种演变的结果。
The analysis of the rotational structure of vibrational and vibronic bands of non-linear molecules presents two kinds of problems which require computer assistance for their solution. One is the amount of data involved. Examples are often encountered where more than 1000 resolved lines can be assigned. The other problem is the complexity of the model Hamiltonians for the two states involved in the transitions. Since relatively high j and K values are frequently involved in such spectra, the Hamiltonians must include sextic centrifugal distortion terms in order to achieve a proper representation of experimental data of optical precision (2 0.001 cm-‘). Further, the method of calculating the eigenvalues and eigenfunctions involves diagonalizing the matrix representation of the Hamiltonian in a basis of symmetric rotor functions. Typically, this involves one hundred matrices of dimensions from 1 to 25. The original program contained the minimum necessary for the least-squares improvement of the parameters of the Hamiltonian but, as its use became more frequent, it was perceived that it could be transformed into a ‘black box’which a spectroscopist could use without excessive requirements for competence in programming and computer management. It is the outcome of this evolution which we describe in this paper.