Ab initio molecular dynamics study of solvated electrons in methanol clusters

Area of Science:

• Physical Chemistry
• Computational Chemistry
• Chemical Physics

Background:

• Methanol cluster anions [(CH3OH)n]- exhibit complex electronic structures.
• Understanding electron binding states is crucial for characterizing these anions.

Purpose of the Study:

• To investigate the physical properties and electron dynamics of small methanol cluster anions using ab initio molecular dynamics.
• To explore the stability and potential isomers of electron states in methanol clusters.

Main Methods:

• Ab initio molecular dynamics simulations were performed for methanol cluster anions (n = 8-32).
• Excess electrons were introduced into neutral clusters in either interior cavity or surface-bound states.
• Computed binding energies were compared with experimental vertical detachment energies.

Main Results:

• Simulated binding energies closely matched experimental vertical detachment energies.
• Interior state electrons were observed to migrate to and stabilize on the surface.
• Relaxed surface states were found to be more stable than experimentally observed states, suggesting new isomers.

Conclusions:

• The study predicts the existence of novel, more stable relaxed surface state isomers of methanol cluster anions.
• Experimental identification of these relaxed states is anticipated to be challenging due to kinetic metastability.
• The excess electron's charge distribution is stabilized by hydroxyl and methyl hydrogens in these predicted states.