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Few compounds act as strong acids. A far greater number of compounds behave as weak acids and only partially react with water, leaving a large majority of dissolved molecules in their original form and generating a relatively small amount of hydronium ions. Weak acids are commonly encountered in nature, being the substances partly responsible for the tangy taste of citrus fruits, the stinging sensation of insect bites, and the unpleasant smells associated with body odor. A familiar example of a...
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The ionic association is the association of oppositely charged ions in an electrolyte solution to form ion pairs. Bjerrum defined ion pairs as two oppositely charged ions whose electrostatic attraction exceeds the thermal energy of the system, typically expressed as 2kT. Electrostatic attraction depends on ionic charge, separation distance, and the dielectric constant of the medium. Thermal energy, represented by kT, reflects the tendency of ions to move independently due to molecular motion.
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1,3,5-Triphenylbenzene and Corannulene as Electron Receptors for Lithium Solvated Electron Solutions
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A molecular perspective on lithium-ammonia solutions.

Eva Zurek1, Peter P Edwards, Roald Hoffmann

  • 1Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, Ithaca, NY 14853, USA.

Angewandte Chemie (International Ed. in English)
|October 13, 2009
PubMed
Summary

Molecular orbital analysis reveals H-->H bonding in lithium-ammonia solutions, explaining the characteristic blue color. Singlet states are more stable than spin-unpaired states.

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Area of Science:

  • Computational chemistry
  • Physical chemistry
  • Solution chemistry

Background:

  • Lithium-ammonia solutions exhibit a distinct blue color, historically observed and attributed to solvated species.
  • Understanding the electronic structure of these solutions is crucial for explaining their unique properties.

Purpose of the Study:

  • To perform a detailed molecular orbital (MO) analysis of various species in lithium-ammonia solutions.
  • To elucidate the electronic properties and bonding interactions within these systems.
  • To explain the origin of the observed optical absorption spectra.

Main Methods:

  • Density Functional Theory (DFT) calculations, specifically Time-Dependent DFT (TD-DFT).
  • Analysis of molecular orbital structures and electronic configurations.
  • Investigation of solvated electrons, monomeric species, and ion-pairs.

Main Results:

  • Identified a stabilizing H-->H bonding interaction involving singly occupied MOs.
  • Found singlet states (S=0) to be energetically favored over spin-unpaired states (S=1, 2...).
  • Calculated electronic excitations responsible for optical absorption, showing metal independence and explaining the absorption tail into the visible spectrum.

Conclusions:

  • The H-->H bonding is a key stabilizing feature in lithium-ammonia solutions.
  • The electronic transitions from the SOMO to p-like levels account for the characteristic blue color observed.
  • The findings provide a fundamental understanding of the electronic structure and optical properties of these solutions.