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In order to 'see' the equilibrium condition of MOS capacitor, do one of the two things: (1) click on "Form the Junction" button followed by "Equilibrate" button; or (2) mouse drag the M, O and S pieces together.
The equilibration process begins with charges around the O-Si interface: (Qox) + (Qch or Qb) = 0. This is purely an arbitrary situation that I viewed as the most 'natural' starting condition. The equilibration process ends with the the condition: EFM in the gate metal = EFS in the Si.
Points to notice: