Raman optical activity spectra: basis set and electron correlation effects |
| |
Authors: | MAGDALENA PECUL ANTONIO RIZZO |
| |
Institution: | 1. Department of Chemistry , University of Warsaw , Pasteura 1, 02-093, Warsaw, Poland;2. Istituto per i Processi Chimico-Fisici del CNR , Area della Ricerca di Pisa, Via Moruzzi 1, 1-56124, Pisa, Italy;3. Istituto per i Processi Chimico-Fisici del CNR , Area della Ricerca di Pisa, Via Moruzzi 1, 1-56124, Pisa, Italy |
| |
Abstract: | Raman and vibrational Raman optical activity (ROA) spectra have been calculated for three molecules: H2O2, CHDTF and CHDTOH. The effects of electron correlation on the ROA parameters of these relatively small systems have been investigated by means of the multiconfigurational self-consistent field (SCF) approach. A range of correlation-consistent basis sets has been used in the calculations. The basis set convergence of the calculated ROA parameters is fairly well achieved when sets of at least d-aug-cc-pVTZ quality are used. On the other hand, the aug-cc-pVDZ set seems to be sufficient for a qualitative analysis. Diffuse functions, possibly a double set, are essential to ensure a good quality of the calculated ROA spectrum. In most cases the sign and approximate magnitude of the ROA are correctly predicted at the SCF level, and the corresponding ROA spectra should be considered qualitatively accurate. |
| |
Keywords: | |
|
|