Effects of static spectrum removal and noise on 2D-correlation spectra of kinetic data

The applicability of two-dimensional (2D) correlation spectroscopy to kinetic data is demonstrated. The photodecomposition of Mo(CO)(6) was used as a model kinetic system. The effects of the steady-state and time-average methods for static spectrum removal were evaluated. The time-average method provided 2D-correlation spectra that were more easily interpreted. The influence of noise was evaluated with the synthetic data. The methods of static spectral removal were affected differently by the presence of noise and the time-average method was detrimentally affected by noise. A low-pass Fourier filtering method was devised to remove noise in the 2D-correlation spectra. Kinetic simulations were demonstrated as useful tools for interpretation of noisy data. (C) 1998 Elsevier Science B.V.