Ammoniated electron as a solvent stabilized multimer radical anion

The excess electron in liquid ammonia ("ammoniated electron") is commonly viewed as a cavity electron in which the s-type wave function fills the interstitial void between 6-9 ammonia molecules. Here we examine an alternative model in which the ammoniated electron is regarded as a solvent stabilized multimer radical anion, as was originally suggested by Symons [Chem. Soc. Rev. 1976, 5, 337]. In this model, most of the excess electron density resides in the frontier orbitals of N atoms in the ammonia molecules forming the solvation cavity; a fraction of this spin density is transferred to the molecules in the second solvation shell. The cavity is formed due to the repulsion between negatively charged solvent molecules. Using density functional theory calculations for small ammonia cluster anions in the gas phase, it is demonstrated that such core anions would semi-quantitatively account for the observed pattern of Knight shifts for 1-H and 14-N nuclei observed by NMR spectroscopy and the downshifted stretching and bending modes observed by infrared spectroscopy. It is speculated that the excess electrons in other aprotic solvents (but not in water and alcohols) might be, in this respect, analogous to the ammoniated electron, with substantial transfer of the spin density into the frontier N and C orbitals of methyl, amino, and amide groups forming the solvation cavity.Comment: 34 pages, 12 figures; to be submitted to J Phys Chem

Ab-initio molecular dynamics of protonated dialanine and comparison to infrared multiphoton dissociation experiments

International audienceFinite temperature Car-Parrinello molecular dynamics simulations are performed for the protonated dialanine peptide in vacuo, in relation to infrared multiphoton dissociation experiments. The simulations emphasize the flexibility of the different torsional angles at room temperature and the dynamical exchange between different conformers which were previously identified as stable at 0 K. A proton transfer occurring spontaneously at the N-terminal side is also observed and characterized. The theoretical infrared absorption spectrum is computed from the dipole time correlation function, and, in contrast to traditional static electronic structure calculations, it accounts directly for anharmonic and finite temperature effects. The comparison to the experimental infrared multiphoton dissociation spectrum turns out very good in terms of both band positions and band shapes. It does help the identification of a predominant conformer and the attribution of the different bands. The synergy shown between the experimental and theoretical approaches opens the door to the study of the vibrational properties of complex and floppy biomolecules in the gas phase at finite temperature

Molecular Density Functional Theory of Water

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