Methanol clusters (CH3OH)n, n = 3-6 in external electric fields: density functional theory approach

Area of Science:

• Physical Chemistry
• Computational Chemistry
• Molecular Physics

Background:

• Methanol clusters exhibit complex structures stabilized by hydrogen bonds.
• The influence of external electric fields on molecular clusters is crucial for understanding their behavior.

Purpose of the Study:

• To investigate the structural evolution of cyclic and branched-cyclic methanol clusters under an applied static electric field.
• To characterize the transitions and their impact on hydrogen bonding and molecular properties.

Main Methods:

• Density Functional Theory (DFT) calculations were employed.
• Simulations analyzed methanol clusters (3-6 molecules) with and without an electric field.

Main Results:

• Electric fields stretch and break intermolecular hydrogen bonds in methanol clusters at threshold values (0.009-0.016 a.u.).
• Structural transitions lead to lower energy linear or branched forms, accompanied by abrupt increases in dipole moment.
• The number of hydrogen bonds decreases with increasing field strength, and vibrational spectra show OH blueshifts and CO redshifts.

Conclusions:

• Applied electric fields induce significant structural changes in methanol clusters, disrupting their hydrogen-bonded networks.
• The observed effects, including vibrational shifts, are more pronounced in methanol clusters than in analogous water clusters.