Spectroscopic properties of dipicolinic acid and its dianion

If robust spectroscopic techniques are to be developed for the detection and identification of pathogens, one must understand the relevant spectroscopic properties of the target molecules. In this paper, we employ density functional theory (DFT) to study the structural, electronic, vibrational.. optical, and magnetic properties of dipicolinic acid (DPA) and its dianion DPA(-2). Our full geometrical optimization and Mulliken charge analysis show that DFT does not lead to the significant discrepancies between charges on symmetric carbon, hydrogen, and oxygen atoms that are found in less accurate calculations based on the complete active space MCSCF method. Our calculated vibrational frequencies, Raman spectra, and infrared spectra for ground-state DPA and DPA(-2) are in good agreement with experiment, and this is also true of the four calculated C-13 NMR spectral lines (for alpha, beta, gamma, and carboxyl sites). Our time-dependent DFT study of the optical excitation and absorption of both DPA and DPA(-2) provides the first interpretation of the observed near ultraviolet absorption and fluorescence spectra. Finally, we discuss for the first time the effect of a solvent on the spectral properties of DPA. (c) 2005 Elsevier B.V. All rights reserved.