Vibrational spectra and harmonic force fields of pyrrolidine derivatives

Comparison between HF, MP2 and DFT force fields

F. Billes, Ekkehard Geidel

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

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 Møller-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.

Original languageEnglish
Pages (from-to)2537-2551
Number of pages15
JournalSpectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
Volume53
Issue number14
Publication statusPublished - Dec 1997

Fingerprint

Vibrational spectra
vibrational spectra
field theory (physics)
Density functional theory
density functional theory
Derivatives
harmonics
deviation
Molecular structure
Stretching
Raman scattering
Infrared radiation
molecular structure
infrared spectra
methylidyne
Raman spectra
pyrrolidine
Experiments
N-methylpyrrolidine

Keywords

  • Assignment of fundamentals
  • Density functional theory
  • Pyrrolidine derivatives
  • Scale factors
  • Vibrational analysis

ASJC Scopus subject areas

  • Spectroscopy

Cite this

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abstract = "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 M{\o}ller-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.",
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AU - Billes, F.

AU - Geidel, Ekkehard

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N2 - 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 Møller-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.

AB - 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 Møller-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.

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