It depends on a lot on the wavelength of the laser, pulse width and the nature of the substrate. Photochemical or photothermal processes will occur depending on the parameters. Once you provide me the details of the process we can proceed further with the answer
The concern here is whether the process of electron-neutral and electron-ion inverse bremsstrahlung absorption at the initial stage is in thermo-chemical equilibrium or not.
I think, the question was not related to creating the breakdown, which obviously depends on the wavelength, pulse width, pulse energy and some other optical property.
Whereas, It was related to the process just after the energy deposition. What kind of equilibrium assumption will be better for the macroscopic point of view for numerical analysis? (Thermodynamic or Thermo-chemical!)