Anharmonic vibrational analysis of 3,4-diaminopyridine and 3-aminopyridine by density functional theory calculations.

J Karpagam, N Sundaraganesan, S Kalaichelvan, S Sebastian

Index: Spectrochim. Acta. A. Mol. Biomol. Spectrosc. 76(5) , 502-12, (2010)

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Abstract

In this work, we will report a combined experimental and theoretical study on molecular structure and vibrational analysis of 3,4-diaminopyridine (3,4-DAP) and 3-aminopyridine (3-AP). The Fourier transform infrared and Fourier transform Raman spectra of 3,4-DAP were recorded in the solid phase. The molecular geometry, harmonic vibrational wavenumbers of 3-AP and 3,4-DAP in the ground-state have been calculated by using MP2 and density functional methods (B3LYP) using 6-311++G(d,p) as basis set. Predicted electronic absorption spectra 3,4-DAP from TD-DFT calculation have been analyzed comparing with the experimental UV-vis spectrum. The calculated HOMO and LUMO energies show that charge transfer occur in the molecule. A detailed interpretation of the infrared spectra of 3-AP and 3,4-DAP is reported. The theoretical spectrograms for FTIR and FT-Raman spectra of the title molecules have also been constructed. Comparison of the experimental spectra with anharmonic vibrational wavenumbers indicates that B3LYP results are more accurate.Copyright 2010 Elsevier B.V. All rights reserved.