Kinetics of inherent processes counteracting crystallization in supercooled monatomic liquid

Area of Science:

• Physical Chemistry
• Materials Science
• Thermodynamics

Background:

• Crystallization involves competing particle attachment (g+) and detachment (g-) rates.
• The detailed balance condition only applies at the critical nucleus size (nc).

Purpose of the Study:

• To define a correspondence rule between g+ and g- for all nucleus sizes (N).
• To calculate g- for supercooled Lennard-Jones liquid across various supercooling levels and nucleus sizes.

Main Methods:

• Derivation of a novel correspondence rule for crystallization kinetics.
• Calculation of detachment rates (g-) for a supercooled Lennard-Jones liquid.
• Formulation of a new kinetic equation for nucleus size distribution.

Main Results:

• The correspondence rule holds true for all stages of crystallization: nucleation, growth, and coalescence.
• Calculated g- is only approximately 2% less than g+ across a wide range of nucleus sizes (N ∈ [nc; 40nc]).
• Detachment processes remain significant throughout crystallization.

Conclusions:

• The established correspondence rule provides a more comprehensive understanding of crystallization kinetics.
• The findings suggest a revised kinetic model, offering an alternative to the Becker-Döring-Zeldovich-Frenkel equation.