Solving complex photocycle kinetics. Theory and direct method.
Solving complex photocycle kinetics. Theory and direct method.
复制标题
解决复杂的光循环动力学。
DOI：
10.1016/s0006-3495(91)82241-x
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发表时间：
1991
影响因子：
3.4
通讯作者：
Nagle,JF
中科院分区：
文献类型：
--
作者：
Nagle,JF
一个直接的非线性最小二乘法描述，获得真正的动力学速率常数和温度无关的光谱n中间体从可见光在三个或更多的温度下的光谱数据。理论分析，这是独立的直接方法的实施，证明了良好的确定的本地解决方案是不可能的少于三个温度。该分析还证明，超过n个波长的测量是多余的，尽管直接方法表明，如果测量n + m个波长（其中m为一阶），则收敛速度更快。这表明测量应该集中在少数测量波长的高精度上，而不是许多波长的低精度。在全局范围内，会出现错误的解决方案，并且拒绝这些解决方案的能力取决于数据的精度，如显式示例所示。本文还提出了一种分析振动光谱数据的优化方法。这样的数据产生独特的结果，这是非常准确的那些从可见光中取得的数据与可比的噪音。它讨论了如何使用这两种数据是有利的，如果在可见光的数据是显着较少的噪音。
A direct nonlinear least squares method is described that obtains the true kinetic rate constants and the temperature-independent spectra of n intermediates from spectroscopic data taken in the visible at three or more temperatures. A theoretical analysis, which is independent of implementation of the direct method, proves that well determined local solutions are not possible for fewer than three temperatures. This analysis also proves that measurements at more than n wavelengths are redundant, although the direct method indicates that convergence is faster if n + m wavelengths are measured, where m is of order one. This suggests that measurements should concentrate on high precision for a few measuring wavelengths, rather than lower precision for many wavelengths. Globally, false solutions occur, and the ability to reject these depends upon the precision of the data, as shown by explicit example. An optimized way to analyze vibrational spectroscopic data is also presented. Such data yield unique results, which are comparably accurate to those obtained from data taken in the visible with comparable noise. It is discussed how use of both kinds of data is advantageous if the data taken in the visible are significantly less noisy.