Microscopic Solvation and Gas-Phase Cluster Chemistry: Bridge the Gap between Isolated Molecules and Condensed Phase

Gas-phase salt bridge interactions between glutamic acid and arginine.

The gas-phase side chain-side chain (SC-SC) interaction and possible proton transfer between glutamic acid (Glu) and arginine (Arg) residues are studied under low-temperature conditions in an overall neutral peptide. Conformation-specific IR spectra, obtained with the free electron laser FELIX, in combination with density functional theory (DFT) calculations, provide insight into the occurrence...

Cluster phase chemistry: gas-phase reactions of anionic sodium salts of dicarboxylic acid clusters with water molecules.

A homologous series of anionic gas-phase clusters of dicarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid) generated via electrospray ionization (ESI) are investigated using collision-induced dissociation (CID). Sodiated clusters with the composition (Na(+))(2)(n+1)(dicarboxylate(2-)(n+1) for singly charged anionic clusters, where n = 1-4, are observed as...

Chapter 4. Cluster Phase Chemistry: Gas Phase Reactions of Anionic Sodium Salts of Dicarboxylic Acid Clusters with Water Molecules

Relationship between quantum decoherence times and solvation dynamics in condensed phase chemical systems

A relationship between the time scales of quantum coherence loss and short-time solvent response for a solute/bath system is derived for a Gaussian wave packet approximation for the bath. Decoherence and solvent response times are shown to be directly proportional to each other, with the proportionality coefficient given by the ratio of the thermal energy fluctuations to the fluctuations in the...

Superelectrophilic chemistry in the gas phase*

Superelectrophilic chemistry in the gas phase is driven by the high intrinsic reactivity of dications. The formation of new doubly charged products proceeds via highly internally excited intermediates. Conditions for the formation of the doubly charged intermediates and a “cooling principle” in the reactivity of dications are explained. The reactivity is demonstrated with several examples.