Gas-Phase Vibrational Spectroscopy and Ab Initio Study of Organophosphorous Compounds: Discrimination between Species and Conformers
journal contributionposted on 02.10.2008, 00:00 by A. Cuisset, G. Mouret, O. Pirali, P. Roy, F. Cazier, H. Nouali, J. Demaison
Gas phase vibrational spectra of dimethyl methylphosphonate (DMMP), trimethyl phosphate (TMP), and triethyl phosphate (TEP) have been measured using FTIR spectroscopy. For DMMP, TMP, and TEP, most of the infrared active vibrational modes have been observed in the 50−5000 cm−1 spectral range, allowing an unambiguous discrimination between the three molecules. The vibrational analysis of the spectra was performed by comparing with MP2 and B3LYP harmonic and anharmonic force field ab initio calculations. The extension to anharmonic calculations provides the best agreement for the mid-infrared and the near-infrared spectra, but they do not improve the harmonic frequency predictions in the far-infrared domain. This part of the vibrational spectra associated with collective and nonlocalized vibrational modes presents the largest frequency differences between the two lowest energy conformers of DMMP and TMP. These two conformers were taken into account in the vibrational assignment of the spectra. Their experimental evidence was obtained by deconvoluting vibrational bands in the mid-infrared and in the far-infrared regions, respectively. For TEP, the conformational landscape appears very complicated at ambient temperature, and a further analysis at low temperature is required to explain the vibrational features of each conformer.
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deconvoluting vibrational bandsenergy conformersConformersGas phase vibrational spectraOrganophosphorous CompoundsFTIR spectroscopynonlocalized vibrational modesfrequency predictionsvibrational modestriethyl phosphateMP 2TMPanharmonic calculationsTEPvibrational analysisambient temperaturedimethyl methylphosphonateDMMPfrequency differencesAb Initio Studyvibrational spectraB 3LYPanharmonic force field ab initio calculationsvibrational assignmentvibrational features