Activated Instability of Homogeneous Bubble Nucleation and Growth

For the superheated Lennard-Jones liquid, the free energy of forming a bubble with a given particle number and volume is calculated using density-functional theory. As conjectured, a consequence of known properties of the critical cavity [S. N. Punnathanam and D. S. Corti, J. Chem. Phys. 119, 10 224 (2003), the free energy surface terminates at a locus of instability. These stability limits reside, however, unexpectedly close to the saddle point. A new picture of homogeneous bubble nucleation and growth emerges from our study, being more appropriately described as an "activated instability."