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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >kv Correlation Analysis. A Quantitative Two-Dimensional IR Correlation Method for Analysis of Rate Processes with Exponential Functions
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kv Correlation Analysis. A Quantitative Two-Dimensional IR Correlation Method for Analysis of Rate Processes with Exponential Functions

机译：kv相关分析。具有指数函数的速率过程分析的二维二维红外相关方法

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摘要

A modified two-dimensional infrared correlation technique called k correlation analysis is introduced. In this method, a mathematical asynchronous cross-correlation is performed between a set of N infrared spectra undergoing a dynamic intensity variation against a set of exponential functions that encompass a user-defined range of rate constants. The observed correlation intensities are a function of the rate constant of the exponential function and the spectral frequency. The kv correlation plots reveal the rate relationships between different molecular groups in terms of a quantitative and tangible parameter, kv, which is the rate constant of the exponential function used in the correlation. A new parameter, the effective rate constant, k_(eff), is defined as the point of maximum correlation intensity at particular frequencies in the plot of k vs v. The calculated values of keff represent the relative rates at which the intensities of the spectral bands change during the course of the dynamic experiment. As a result, these keff values are comparable and can be used to assign quantitative rate relationships. By using simulated IR spectra, it was shown that the keff parameter is sensitive to the relative order in which the intensity change occurs, while the size of the correlation peaks gives an indication of the magnitude of the intensity change. Spectral bands whose rate of intensity change varies through a dynamic data set are distinguished by the presence of both positive and negative peaks in the kv correlation plots. We applied the kv correlation analysis method to the time-dependent IR spectra of the photoinitiated polymerization reaction of ethyl 2-cyanoacrylate. Analysis of the keff effective rate constants showed that vibrational modes corresponding to the monomeric and polymeric cyanoacrylate molecules react differently depending on whether an inhibitor is present.
机译：介绍了一种改进的二维红外相关技术，称为k相关分析。在这种方法中，在经历了动态强度变化的一组N个红外光谱与一组包含用户定义的速率常数范围的指数函数之间进行数学异步互相关。观察到的相关强度是指数函数的速率常数和频谱频率的函数。 kv相关图根据定量和有形参数kv揭示了不同分子组之间的速率关系，kv是相关中使用的指数函数的速率常数。一个新的参数，即有效速率常数k_（eff），被定义为在k与v曲线图中特定频率下最大相关强度的点。keff的计算值代表频谱强度的相对速率。在动态实验过程中，谱带发生变化。结果，这些keff值是可比较的，可用于分配定量速率关系。通过使用模拟的红外光谱，表明keff参数对强度变化发生的相对顺序敏感，而相关峰的大小则指示了强度变化的幅度。强度变化率通过动态数据集变化的光谱带通过在kv相关图中存在正峰和负峰来区分。我们将kv相关分析方法应用于2-氰基丙烯酸乙酯的光引发聚合反应的时间依赖性红外光谱。 keff有效速率常数的分析表明，取决于是否存在抑制剂，对应于单体和聚合氰基丙烯酸酯分子的振动模式反应不同。

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