Gas-phase vibrational spectroscopy and ab initio study of organophosphorus compounds: discrimination between species and conformers. 2008

A Cuisset, and G Mouret, and O Pirali, and P Roy, and F Cazier, and H Nouali, and J Demaison
Laboratoire de Physico-Chimie de l'Atmosphère CNRS UMR 8101, Université du Littoral Côte d'Opale, 189 A Ave. Maurice Schumann, Dunkerque, France. arnaud.cuisset@univ-littoral.fr

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.

UI MeSH Term Description Entries
D008968 Molecular Conformation The characteristic three-dimensional shape of a molecule. Molecular Configuration,3D Molecular Structure,Configuration, Molecular,Molecular Structure, Three Dimensional,Three Dimensional Molecular Structure,3D Molecular Structures,Configurations, Molecular,Conformation, Molecular,Conformations, Molecular,Molecular Configurations,Molecular Conformations,Molecular Structure, 3D,Molecular Structures, 3D,Structure, 3D Molecular,Structures, 3D Molecular
D009943 Organophosphorus Compounds Organic compounds that contain phosphorus as an integral part of the molecule. Included under this heading is broad array of synthetic compounds that are used as PESTICIDES and DRUGS. Organophosphorus Compound,Organopyrophosphorus Compound,Organopyrophosphorus Compounds,Compound, Organophosphorus,Compound, Organopyrophosphorus,Compounds, Organophosphorus,Compounds, Organopyrophosphorus
D010755 Organophosphates Carbon-containing phosphoric acid derivatives. Included under this heading are compounds that have CARBON atoms bound to one or more OXYGEN atoms of the P( Organophosphate,Phosphates, Organic,Phosphoric Acid Esters,Organopyrophosphates,Acid Esters, Phosphoric,Esters, Phosphoric Acid,Organic Phosphates
D011312 Pressure A type of stress exerted uniformly in all directions. Its measure is the force exerted per unit area. (McGraw-Hill Dictionary of Scientific and Technical Terms, 6th ed) Pressures
D011789 Quantum Theory The theory that the radiation and absorption of energy take place in definite quantities called quanta (E) which vary in size and are defined by the equation E Quantum Theories,Theories, Quantum,Theory, Quantum
D005740 Gases The vapor state of matter; nonelastic fluids in which the molecules are in free movement and their mean positions far apart. Gases tend to expand indefinitely, to diffuse and mix readily with other gases, to have definite relations of volume, temperature, and pressure, and to condense or liquefy at low temperatures or under sufficient pressure. (Grant & Hackh's Chemical Dictionary, 5th ed)
D013696 Temperature The property of objects that determines the direction of heat flow when they are placed in direct thermal contact. The temperature is the energy of microscopic motions (vibrational and translational) of the particles of atoms. Temperatures
D014732 Vibration A continuing periodic change in displacement with respect to a fixed reference. (McGraw-Hill Dictionary of Scientific and Technical Terms, 6th ed) Vibrations
D014835 Volatilization A phase transition from liquid state to gas state, which is affected by Raoult's law. It can be accomplished by fractional distillation. Vaporization,Volatility
D017550 Spectroscopy, Fourier Transform Infrared A spectroscopic technique in which a range of wavelengths is presented simultaneously with an interferometer and the spectrum is mathematically derived from the pattern thus obtained. FTIR,Fourier Transform Infrared Spectroscopy,Spectroscopy, Infrared, Fourier Transform

Related Publications

A Cuisset, and G Mouret, and O Pirali, and P Roy, and F Cazier, and H Nouali, and J Demaison
October 2007, The Journal of chemical physics,
A Cuisset, and G Mouret, and O Pirali, and P Roy, and F Cazier, and H Nouali, and J Demaison
April 2005, The Journal of chemical physics,
A Cuisset, and G Mouret, and O Pirali, and P Roy, and F Cazier, and H Nouali, and J Demaison
May 2018, Chimia,
A Cuisset, and G Mouret, and O Pirali, and P Roy, and F Cazier, and H Nouali, and J Demaison
December 2022, The journal of physical chemistry. A,
A Cuisset, and G Mouret, and O Pirali, and P Roy, and F Cazier, and H Nouali, and J Demaison
June 2004, The Journal of chemical physics,
A Cuisset, and G Mouret, and O Pirali, and P Roy, and F Cazier, and H Nouali, and J Demaison
May 2011, Journal of molecular modeling,
A Cuisset, and G Mouret, and O Pirali, and P Roy, and F Cazier, and H Nouali, and J Demaison
May 2006, The Journal of chemical physics,
A Cuisset, and G Mouret, and O Pirali, and P Roy, and F Cazier, and H Nouali, and J Demaison
April 2005, The journal of physical chemistry. B,
A Cuisset, and G Mouret, and O Pirali, and P Roy, and F Cazier, and H Nouali, and J Demaison
August 2007, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy,
A Cuisset, and G Mouret, and O Pirali, and P Roy, and F Cazier, and H Nouali, and J Demaison
February 2015, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy,
Copied contents to your clipboard!