What is Ambient Occlusion?
Standard lighting models compute the color of a surface based on its properties and the lights in a scene. Objects that are in the path of a light cast shadows; otherwise, their presence does not affect the lighting of other objects. Ambient occlusion improves this model by accounting for the dimming caused by objects that block out ambient light. An example of this is the junction where a wall and a ceiling meet; while no direct shadows are cast, the corner nevertheless appears darker. Ambient occlusion simulates this phenomenon, along with all other cases where objects are close enough to block out ambient light.
What does it look like?
See below for the first comparison in the game title Half Life 2