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This material contains in itself the initial 2 V-Ray materials - the floor's and the walls' ones. So now assigned on the floor object, V-Ray knows that while calculating the GI it has to use the GI material (in our case: walls - VRayMtl with Diffuse Color (200, 200, 200)) and during rendering it uses the Base material (in our case: floor - VrayMtl with VRayMtl with texture in the Diffuse Slot). The result of that is quite different from the previous render as the Color Bleeding has gone. Of course this depends entirely on our choice for the GI material. For instance, if we had chosen a bluish colored material, the final result would also be tinted slightly to blue, like in the first render with the pale brown colors.
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Now each of the chairs has a different material assigned in their VRayOverride Reflect material. The first one has a green diffuse color, the second one has black, the third one has blue, the fourth - purple, and the fifth has a red diffuse color. V-Ray uses those materials when the objects are seen in reflections. In our scene, the environment is actually a reflective surface, so the chairs are being reflected. On the other hand, you can also notice that the base material of the chairs is also reflective, and the fourth chair is seen with its Override Reflection material Reflect material in the middle chair.
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The next render is even more complex as the chairs' Override Refraction Material is Override Refract material is activated as well. From left to right follow: a blue and a red diffuse color. Those materials are set so that when seen through refraction, V-Ray considers and renders the objects with them. As you can see the Reflection the Reflect materials are still affecting the render image.
If you take a closer look at the glass chairs' edges you will notice the green reflection, which is actually the reflection reflect material of the right chair. While V-Ray had been tracing the rays on the chairs' surfaces, those polygons on the edges had first captured a reflection, so that's why there are green traces.
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