Vibrational spectra and harmonic force fields of pyrrolidine derivatives: comparison between HF, MP2 and DFT force fields
| Autor: | Ferenc Billes, E. Geidel |
|---|---|
| Rok vydání: | 1997 |
| Předmět: |
Infrared
Chemistry Ab initio Molecular physics Atomic and Molecular Physics and Optics Spectral line Analytical Chemistry symbols.namesake Normal mode Computational chemistry Physics::Atomic and Molecular Clusters symbols Harmonic Density functional theory Raman spectroscopy Instrumentation Spectroscopy Basis set |
| Zdroj: | Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 53:2537-2551 |
| ISSN: | 1386-1425 |
| Popis: | Infrared and Raman spectra are reported for the isotopic species of pyrrolidine-d0 (PY) and -d1 and for N-methylpyrrolidine-d0 (NMP), -d2, -d3 and -d8. A complete assignment of the experimentally observed bands to normal modes is presented and discussed in particular in the CH/CD stretching region. The molecular structures and harmonic force fields were calculated ab initio at the Hartree–Fock (HF), the second order Moller–Plesset (MP2) and the density functional theory (DFT) level with the 6-31G* basis set. The force fields were fitted by use of 7 (PY) and 4 (NMP) independent scale factors. The spectra calculated with the DFT force fields are in better agreement with the experiment than those calculated by the MP2 and HF force fields. Though some scaled fundamental frequencies show larger deviations from the experimental ones, the mean percentage deviations of calculated frequencies from experimental fundamentals are less than 2.6% for all isotopic species of PY and NMP under study. The results indicate that density functional theory is a reliable tool to get a deeper insight in the assignment of vibrational spectra and the nature of normal modes of pyrrolidine derivatives. |
| Databáze: | OpenAIRE |
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