Etude des spectres de vibration et analyse en coordonnées normales des oxydes de triméthylamme, triméthylphosphine et triméthylarsine

Choplin, F.; Kaufmann, G.

doi:10.1016/0584-8539(70)80151-9

Cited by 41 publications

(9 citation statements)

References 15 publications

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“…The experimental values for TCPO [43], DMMP [44] and Sarin (an estimate [3] based on data for the liquid [2]) are all for the gas phase and can be compared directly with the computed results. On the other hand TMPO is a solid, and infrared data were obtained for a powder dispersed in mineral oil [45]. m(P@O) is known to be significantly red-shifted in the condensed phase due to intermolecular interactions, which are not included in the calculation.…”

Section: Free-molecule Structures Vibrational Frequencies and Ionizamentioning

confidence: 99%

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Energy-level alignment in the adsorption of phosphonyl reagents on γ-Al2O3

Bermudez

2008

Surface Science

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Section: Free-molecule Structures Vibrational Frequencies and Ionizamentioning

confidence: 99%

“…To our knowledge, no corresponding structural parameters are available [43], DMMP [44] and Sarin are from gas phase infrared spectra. The TMPO value is for the solid [45]. The Sarin value is an estimate [3] based on data for the liquid [2].…”

Section: Cluster Models For C-al 2 Omentioning

confidence: 99%

Energy-level alignment in the adsorption of phosphonyl reagents on γ-Al2O3

Bermudez

2008

Surface Science

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“…Early spectroscopic studies involving TMAO concentrated on establishing its geometry and molecular properties. Properties of interest to these early researchers included TMAO’s dipole moment, bond properties, force constants, and symmetry. − The dipole moment of TMAO has been studied extensively because of its magnitude being fairly large, indicating a semipolar bond . Over the years TMAO’s dipole moment has been measured and calculated by many different methods. ,,,,− The N–O bond length is also of interest in characterizing the physical properties and behavior of TMAO. , Researchers are also interested in the physical properties of TMAO in the biological setting.…”

Section: Introductionmentioning

confidence: 99%

“…Over the years TMAO’s dipole moment has been measured and calculated by many different methods. ,,,,− The N–O bond length is also of interest in characterizing the physical properties and behavior of TMAO. , Researchers are also interested in the physical properties of TMAO in the biological setting. Many spectroscopic studies, including infrared, ,,,− Raman, ,,,− NMR, , UV–vis absorption, circular dichroism, − and gas electron diffraction have been employed over the years to describe TMAO’s molecular properties and help explain the effects of TMAO on hydrogen-bonded water networks and also biological environments in general.…”

Section: Introductionmentioning

confidence: 99%

Raman Spectroscopic Signatures of Noncovalent Interactions Between Trimethylamine N-oxide (TMAO) and Water

2011

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The effects of hydration on vibrational normal modes of trimethylamine N-oxide (TMAO) are investigated by Raman spectroscopy and electronic structure computations. Microsolvated networks of water are observed to induce either red or blue shifts in the normal modes of TMAO with increasing water concentration and to also exhibit distinct spectral signatures. By taking advantage of the selective and gradual nature of the water-induced shifts and using comparisons to theoretical predictions, the assignments of TMAO's normal modes are re-examined and the structure of the hydrogen-bonded network in the vicinity of TMAO is elucidated. Agreement between experiment and theory suggests that the oxygen atom in TMAO accepts on average at least three hydrogen bonds from neighboring water molecules and that water molecules are likely not directly interacting with TMAO's methyl groups.

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“…7c c The calculated n(N-O) IR vibrational frequencies are unscaled.d The n(N-O) IR vibrational frequency for 1 was taken from the literature 13. …”

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confidence: 99%

Bonding situation and N–O-bond strengths in amine-N-oxides—a combined experimental and theoretical study

Rogachev

Burger

2012

Phys. Chem. Chem. Phys.

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The bonding situation and energetics of the N-O bond in a series of amine-N-oxides, Ph(x)(CH(3))(3-x)N-O, where x = 0-3, were analyzed experimentally and theoretically. There is a notable nearly linear decrease of the N-O bond dissociation energies (BDEs) for this series with an increasing number of phenyl groups x. This was investigated experimentally by X-ray high angle multipole refinement techniques in combination with subsequent topological analysis of the electron density for the representative (CH(3))(2)PhN-O, 2, and complementary theoretical calculations at the DFT and multireference CASSCF and MR-perturbation theory (MCQDPT2) levels. Both the theoretical and experimental results unambiguously revealed a polar covalent σ-bond for the N-O bond with an essentially identical bonding situation for all amine-N-oxides studied. This apparent disparity between the bonding situation and the trend of BDEs is attributed to the large differences of the relaxation energies of the corresponding amines Ph(x)(CH(3))(3-x)N, (x = 0-3), respectively, the required preparation energies (ΔE(prep)) for the reverse N-O bond forming process. The detailed theoretical analysis of the amines allowed us to trace the trend of larger values of ΔE(prep) for a higher number of phenyl groups x to an increase of n(N) → π*(C-C) delocalization interactions.

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Etude des spectres de vibration et analyse en coordonnées normales des oxydes de triméthylamme, triméthylphosphine et triméthylarsine

Cited by 41 publications

References 15 publications

Energy-level alignment in the adsorption of phosphonyl reagents on γ-Al2O3

Energy-level alignment in the adsorption of phosphonyl reagents on γ-Al2O3

Raman Spectroscopic Signatures of Noncovalent Interactions Between Trimethylamine N-oxide (TMAO) and Water

Bonding situation and N–O-bond strengths in amine-N-oxides—a combined experimental and theoretical study

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