Resolution enhancement of composite spectra using wavelet-based derivative spectrometry.

An approach based on the using of the continuous wavelet transform (CWT) in derivative spectrometry (DS) is considered. Within the framework of the approach we develop a numerical differentiation algorithm with continuous wavelets for improving resolution of composite spectra. The wavelet-based derivative spectrometry (WDS) method results in best contrast in differential curves compared to the conventional derivative spectrometry method. A main advantage is that, as opposed to DS, WDS gives stable estimations of derivative in the wavelet domain without using the regularization. A wavelet shape and the information redundancy are of the greatest importance when the continuous wavelet transform is used. As an appropriate wavelet we offer to utilize the nth derivative of a component with a priori known shape. The energy distribution into scales allows one to determine a unique wavelet projection and in that way to avoid the information redundancy. A comparative study of WDS and DS with the statistical regularization method (SRM) is made; in particular, limits of applicability of these are given. Examples of the application of both DS and WDS for improving resolution of synthetic composite bands and real-world composite ones coming from molecular spectroscopy are given.

Internal rotation in 1,2-di-(p-XC6H4)ethanes (X=H, Br, NO2): infrared spectra and compensation effect.

Infrared absorption spectra and internal rotation of 1,2-di-(p-XC(6)H(4))ethanes (X=H, Br, NO(2)) in crystalline phase, liquid and solutions at various temperatures have been investigated. Band fitting was applied to conformationally sensitive regions of the spectra, and assignment of the peaks to trans and gauche conformations was performed. Enthalpy and entropy differences of the conformers (deltaH(0) and deltaS(0)) were found to be solvent-dependent, and it is interpreted in terms of previously discovered compensation effect. The values deltaH(0) and deltaS(0) for 1,2-di-(p-NO(2)C(6)H(4))ethane obtained are unusually large.