Negative Activation is only an apparent effect, it is not a real quantity. Very rarely, in reactions that go through some kind of intermediate, the reaction rate is found to be dependent on the equilibrium constant of the rate determining step. If this step is exothermic, the equilibrium constant decreases with increasing temperature. So, even though the rate constant increases with increasing temperature (as it should - this is a sign of positive activation energy), the product of the rate constant and equilibrium constant (or apparent rate constant) may be decreasing with increasing temperature. This is what is referred to as negative activation.
The oxidation of NO to give NO2 is such a reaction.
See : http://www.rod.beavon.clara.net/nitrogenmonoxide.htm