Electron-Driven Acid-Base Chemistry: Proton Transfer from Hydrogen Chloride to Ammonia

  title={Electron-Driven Acid-Base Chemistry: Proton Transfer from Hydrogen Chloride to Ammonia},
  author={Soren N. Eustis and D. Radisic and Kit H. Bowen and Rafał A. Bachorz and Maciej Haranczyk and Gregory K. Schenter and Maciej Gutowski},
  pages={936 - 939}
In contrast to widely familiar acid-base behavior in solution, single molecules of NH3 and HCl do not react to form the ionic salt, NH+4Cl–, in isolation. We applied anion photoelectron spectroscopy and ab initio theory to investigate the interaction of an excess electron with the hydrogen-bonded complex NH3···HCl. Our results show that an excess electron induces this complex to form the ionic salt. We propose a mechanism that proceeds through a dipole-bound state to form the negative ion of… 

The exemplary role of nanoconfinement in the proton transfer from acids to ammonia.

It is demonstrated that this process can be feasible under nanoconfinement without using any solvent molecules, and halide ions except fluoride behave like protons under high confinement, leading to the formation of NH3X instead of NH4 ions.

The onset of electron-induced proton-transfer in hydrated azabenzene cluster anions.

The computations suggest proton transfer to be energetically viable in all five N-heterocyclic systems studied here when three or more water molecules are present, but protontransfer is not observed experimentally in the triazine nor in the diazine series.

Formation of (HCOO-)(H2SO4) Anion Clusters: Violation of Gas-Phase Acidity Predictions.

Analysis of quantum-mechanical calculations indicates that a large proton affinity difference is offset by the gain in intermolecular interaction energy between HCOO- and H2SO4 through the electron delocalization and formation of two strong hydrogen bonds, which renders (HCOOH)(HSO4-) to be the dominant species at higher temperatures.

Proton transfer, electron binding and electronegativity in ammonium-containing systems

Using modern electronic structure methods, the ammonia-hydrogen halide complexes and their anions are characterised to determine the number, type, and properties of their minima, and their electron

C70 Fullerene Cage as a Novel Catalyst for Efficient Proton Transfer Reactions between Small Molecules: A Theoretical study

The interior of C70 is an ideal catalytic platform for proton transfer reactions and the design of related novel materials, suggesting that the inability of current experiments to detect many infrared active vibrational bands of the endo species in these systems is likely to be a consequence of the substantial electrostatic screening effect of the cage.

Single- versus Multi-Proton-Coupled Rydberg-State Electron Transfer in Amine Clusters

Amino fragments (−NH2) are well-known to exist widely in biological systems and their protonated forms are inclined to trap electrons and form Rydberg radicals (−NH3•) in the electron-excess systems.

Importance of Time Scale and Local Environment in Electron-Driven Proton Transfer. The Anion of Acetoacetic Acid.

It is concluded that binding an excess electron in a π* valence orbital changes the localization of a proton in the fully relaxed structure of the AA(-) anion, and the valence anion is named an ol structure.

Realization of Lewis Basic Na Anion in the NaBH3- Cluster.

This study represents the first example of a Lewis adduct with an alkalide as the Lewis base, designed on the principle of minimum-energy rupture, and characterized by a synergy of anion photoelectron spectroscopy and electronic structure calculations.



Direct formation of solid ammonium chloride particles from HCl and NH3 vapors

The possibility of direct formation of particulate ammonium chloride (NH4Cl) from ammonia (NH3) and hydrogen chloride (HCl) gases was investigated by density functional theory and ab initio methods.

Strongly hydrogen-bonded molecular complexes studied by matrix-isolation vibrational spectroscopy. Part 2.—Amine–hydrogen chloride complexes

Infrared spectra are reported of a strongly hydrogen-bonded complex between ammonia and hydrogen chloride trapped in argon and nitrogen matrices. There are substantial differences between the spectra

On the binding of electrons to nitromethane: Dipole and valence bound anions

Conventional (valence) and dipole‐bound anions of the nitromethane molecule are studied using negative ion photoelectron spectroscopy, Rydberg charge exchange and field detachment techniques.

Proton-coupled electron transfer: the mechanistic underpinning for radical transport and catalysis in biology

This discussion will present model systems containing orthogonal ET and PT pathways, thereby allowing the proton and electron tunnelling events to be disentangled and a case study of radical-based quantum catalysis in a natural biological enzyme, class I Escherichia coli ribonucleotide reductase.

Ab initio study of the dipole-bound anion (H2O…HCl)−

The (H2O…HCl)− anion has been studied at the coupled cluster level of theory with single, double, and noniterative, triple excitations whereas lowest energy structures have been determined at the

Proton-coupled electron transfer reactions in solution: Molecular dynamics with quantum transitions for model systems

A general minimal model for proton-coupled electron transfer (PCET) reactions in solution is presented. This model consists of three coupled degrees of freedom that represent an electron, a proton,

AT base pair anions versus (9-methyl-A)(1-methyl-T) base pair anions.

While there may be other pathways for electron-induced DNA alterations, BFPT in the WC/HS configurations of (AT)(-) is not feasible, and the configuration of (MAMT)(-) and its lack of electron- induced proton transfer are inter-related.