Low ionization potentials of binuclear superalkali B(2)Li(11)

Area of Science:

• Computational Chemistry
• Materials Science
• Superatom Chemistry

Background:

• Superalkalis are atomic or molecular species with exceptionally low ionization potentials.
• The electronic shell model has been successful in predicting properties of homonuclear metal clusters.
• Understanding the behavior of doped clusters is crucial for designing new materials.

Purpose of the Study:

• To theoretically predict the existence and properties of a new binuclear superalkali, B(2)Li(11), and its cation, B(2)Li(11)(+).
• To investigate the structural and electronic characteristics of these novel species.
• To explore their potential as building blocks for advanced materials.

Main Methods:

• Density Functional Theory (DFT) calculations were employed to predict structures and properties.
• Optimized geometries and electronic states were determined.
• Vertical electron affinities were calculated using the OVGF/6-311+G(3df) level of theory.

Main Results:

• Six minimum energy structures were identified for B(2)Li(11), with five cation states exhibiting superalkali characteristics.
• The global minima structures of B(2)Li(11) and B(2)Li(11)(+) resemble a capsule with two boron atoms linked centrally.
• Calculated vertical electron affinities for B(2)Li(11)(+) were 3.40–3.73 eV, lower than Cs and mononuclear superalkali BLi(6).

Conclusions:

• The studied B(2)Li(11) species are classified as superalkalies, and B(2)Li(11)(+) as superalkali cations.
• These binuclear superalkalies expand the known family of superatoms and offer potential for creating materials with strong electron donors.
• The electronic shell structure deviates from predictions, highlighting the complexity introduced by doped nonmetal atoms in heteronuclear clusters.