physical chemistry - When simulating spectral line broadening, which convolution is preferred?

Many computational chemistry packages permit the calculation of vibrational and electronic spectra. These spectra are obtained as a set of discrete eigenvalues however they are often convolved with some distribution to give a continuous spectrum that is realistic for a finite temperature, rather than a sequence of impulse functions.

The ADF package allows the user to convolve the spectrum with either a Gaussian or Cauchy (Lorentzian) function. My understanding is that the latter affords a more realistic line broadening, however the Gaussian must be there for a reason.

Which spectral broadening scheme is preferred? Why the choice?

Answer

I'm not familiar with the computational packages -- I'm an experimentalist, not a theoretician.

As an example for why both might be present, we can turn to gaseous infrared spectroscopy: one will quickly find that the line-widths in vibration-rotation spectra depend on pressure. At lower pressures, say less than a torr, Doppler-broadening is the main mechanism. This is Gaussian in nature. While at higher pressures the broadening is instead due to collisions, which are Lorentzian. You'll find combinations of the two and so forth depending on the specifics of your case.