The spectroscopic (FT-IR, FT-IR gas phase, FT-Raman and UV) and NBO analysis of 4-Hydroxypiperidine by density functional method.

S Sebastian, N Sundaraganesan

Index: Spectrochim. Acta. A. Mol. Biomol. Spectrosc. 75(3) , 941-52, (2010)

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Abstract

In this work, we report a combined experimental and theoretical study on molecular structure, vibrational spectra, NBO and UV-spectral analysis of 4-Hydroxypiperidine (4-HP). The FT-IR solid phase (4000-400 cm(-1)), FT-IR gas phase (5000-400 cm(-1)) and FT-Raman spectra (3500-50 cm(-1)) of 4-HP was recorded. The molecular geometry, harmonic vibrational frequencies and bonding features of 4-HP in the ground-state have been calculated by using the density functional methods (BLYP, B3LYP) with 6-311G (d,p) as basis set. The assignments of the vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA) following the Scaled Quantum Mechanical Force Field Methodology (SQMFF). Stability of the molecule arising from hyperconjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The results show that charge in electron density (ED) in the sigma* antibonding orbitals and E (2) energies confirms the occurrence of ICT (Intra-molecular Charge Transfer) within the molecule. The UV spectrum was measured in ethanol solution. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) result complements the experimental findings. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. Finally the calculation results were applied to simulated infrared and Raman spectra of the title compound which show good agreement with observed spectra.Copyright 2009 Elsevier B.V. All rights reserved.