Picky Picky, PICKY!!!You can't make that statement unless you state the actual voltage, all of the conditions and also the duration of the voltage. A voltage of 5.001 exceeds 5.000 volts so will that matter? Actual testing of the type you are getting at is a complex lab environment type of test along with monitoring and recording everything happening. Starting with ambient temperature, ambient RH (Relative Humidity) thermal rise on the part under test until mean failure and the list goes on. Every parameter also needs well defined.
As was pointed out you want to create an Over Voltage Condition, that said you need to define all of your test conditions as well as your test methods and a detailed procedure. That done you need to lest all of your equipment requirements, that is the equipment you plan to use to conduct your test. What you are describing comes under destructive testing since you plan to destroy the part during the testing. You also need to describe in detail how you plan to acquire the data and where you plan to put the data during the test.
So what is your plan and exact goal, that means well defined. I want to apply a high voltage to a PIC Chip is not well defined.