Ab Initio and DFT Predictions of Infrared Intensities and Raman Activities

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 115; no. 1; pp. 63 - 69
• Main Authors: Zvereva, Elena E, Shagidullin, Artur R, Katsyuba, Sergey A
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 13.01.2011
• Subjects: A: Molecular Structure, Quantum Chemistry, General Theory
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp108057p

Relative infrared (IR) intensities and relative Raman activities have been computed for vibrations of test molecules, including from two to nine heavy atoms, using second-order Moller−Plesset perturbation theory (MP2), and three hybrid density functionals (B3LYP, M05, and M05-2X). The basis set convergence of vibrational properties is discussed. Our results demonstrate that B3LYP offers the most cost-effective choice for the prediction of molecular vibrational properties, but the predictions of another two tested hybrid functionals are very similar and in very good agreement with experimental data. MP2 shows good performance for the IR intensities, whereas the quality of prediction of the relative Raman activities should be characterized as only moderate. B3LYP calculations of the relative IR intensities using highly compact Sadlej’s Z3PolX basis set retain the high accuracy of the more CPU expensive Sadlej’s pVTZ and much more expensive aug-cc-pVTZ calculations. Relative Raman activities are more sensitive to basis set effects and require at least Sadlej’s pVTZ to obtain quantitative results.