It’s to do with the movement of the air. If you have a radiator on a wall without a window the warm air will rise on that wall and cause a convection current. This will cause cold air to fall on the window wall causing a cold draft across the floor.
I’ve noticed this even worse when there has been a sofa under the window causing a very noticeable cold draft from under it.
A radiator under a window effectively puts a warm curtain of air in front of the window preventing the cold draft forming.
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