Selective calculation of high-intensity vibrations in molecular resonance Raman spectra

We present an intensity-driven approach for the selective calculation of vibrational modes in molecular resonance Raman spectra. The method exploits the ideas of the mode-tracking algorithm [M. Reiher and J. Neugebauer, J. Chem. Phys. 118, 1634 (2003)] for the calculation of preselected molecular vibrations and of Heller's gradient approximation [Heller et al., J. Phys. Chem. 86, 1822 (1982)] for the estimation of resonance Raman intensities. The gradient approximation allows us to construct a basis vector for the subspace iteration carried out in the mode-tracking calculation, which corresponds to an artificial collective motion of the molecule that contains the entire intensity in the resonance Raman spectrum. Subsequently, the algorithm generates new basis vectors from which normal mode approximations are obtained. It is then possible to provide estimates for (i) the accuracy of the normal mode approximations and (ii) the intensity of these modes in the final resonance Raman spectrum. This approach is tested for the examples of uracil and a structural motif from the E colicin binding immunity protein Im7, in which a few aromatic amino acids dominate the resonance Raman spectrum at wavelengths larger than 240 nm.