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When two face to face contact areas are just being separated to each other.
They do not be separated instantly, contact area on the contact face is being reduced and ultimately comes to a point and then they are finally de-touched. Although this happens in a fraction of micro second but it is the fact.
At this instant of de-touching of contacts in a vacuum, the current through the contacts concentrated on that last contact point on the contact surface and makes a hot spot.
As it is vacuum, the metal on the contact surface is easily vaporized due to that hot spot and create a conducting media for arc path.