Ultra-high resolution near-infrared spectrum by wavelet packet transform revealing the hydrogen bond interactions

Abstract

Resolution is always an obstacle to analyzing the fine structure of a spectrum. The problem is particularly serious in the analysis of the near-infrared (NIR) spectra of aqueous solutions, because the spectrum is generally composed of overlapping broad peaks making the understanding of the structures and the interactions notoriously difficult. In this work, wavelet packet transform (WPT) was adopted to enhance the resolution of the NIR spectra of aqueous mixtures. Due to the microscopic ability of WPT in both position and frequency, the fine details of a spectrum can be observed in the spectral components of different frequencies obtained by WPT decomposition. Ultra-high resolution spectrum can be obtained from the high-frequency component representing the spectral features. Spectral features of different hydrogen-bonded OH, as well as the OH in HOH and HOD, were identified from the high-resolution NIR spectra of water and heavy water mixtures and validated by the variation of the spectral intensity with the mole ratio of H2O and D2O. The high-resolution spectrum was further applied in analyzing the interaction of amine and water. The spectral features of the hydrogen bonding between CH/NH in tert-butylamine (TBA) and OH in water were observed. The structures of CH bonded to one water molecule, and the structures of NH connecting with one and two water molecules were identified.