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With Positron Emission Tomography (PET) it is possible to map brain activity using radioactive glucose.Demonstrating that when brain areas are active they consume more glucose.So yes, thinking does burn a few more calories. http://en.wikipedia.org/wiki/Neuroimaging
I suppose the next question I need to know the answer is...is how many calories does ' thinking ' burn ?....lets say a good 5 minutes deep thought !!
The reversing checkerboard stimulus induced large increases in regional blood flow to visual cortex...activation resulted in a normalized visual cortex CBF increase of 35.6%