Step-scan transient Fourier transform infrared (FT-IR) difference spectra are often measured in an ac-coupled configuration. The resulting differential intensity spectra contain both positive and negative bands. This condition poses problems for direct phase correction by the standard Mertz and Forman methods. Restricting the calculated phase angle to the range [-pi/2, pi/2] was previously shown to fix some of these problems, but we show that the use of a reduced-resolution phase spectrum can produce other artifacts. The effect of reduced resolution is analyzed for a simulated noise-free spectrum and for a measured transient spectrum of a real photochemical system, bacteriorhodopsin. Examination of these results reveals that the Mertz and Mertz Signed methods can produce spectral bands of reduced magnitude and unusual band shape, with considerable amounts of intensity remaining along the imaginary axis after phase correction. However, these errors can be eliminated by self-convolution of the measured interferogram, which doubles all phase angles, prior to smoothing. This procedure removes the potential discontinuities in the phase angle due to sign changes in the differential spectrum. With bacteriorhodopsin, this doubled-angle method for direct phase correction is able to produce a transient spectrum which closely matches that produced by using a separately measured dc interferogram to calculate the phase angle.
You do not have subscription access to this journal. Cited by links are available to subscribers only. You may subscribe either as an OSA member, or as an authorized user of your institution.
Contact your librarian or system administrator
Login to access OSA Member Subscription