No, it is not atmospheric pressure. When we talk about external pressure, we are usually implying a "negative internal" pressure, and is used to describe the effect of the vessel contents experiencing a very instantaneous change of state (liquid to gas). The rapid forming and evacuation of the gas from the vessel creates a vacuum-like effect making the vessel want to implode or collapse inwards. As it is impossible to create a true vacuum condition, we view the loadings as a positive external load inversely equal to the actual negative internal load. In this case, the external load would not be greater than atmospheric conditions. Neglecting sea level elevation, it is widely accepted as 15 psig or 103 kPag.
Reading back over that, I am not convinced my explanation is going to click. Anyone want to elaborate or correct that??
Granted, it can also be applied if the vessel is buried underground or water; it will be subject to an external pressure equal to the loading caused by the water (hydrostatic head) or soil.