Probably the most common silicone of all. It is a polymer (created from repeating subunits) molecule and has different molecular weight and thus different viscosity versions from water-light to thick liquid.
As for skincare, it makes the skin silky smooth, creates a subtle gloss and forms a protective barrier (aka occlusive). Also, works well to fill in fine lines and wrinkles and give skin a plump look (of course that is only temporary, but still, it's nice). There are also scar treatment gels out there using dimethicone as their base ingredient. It helps to soften scars and increase their elasticity.
As for hair care, it is a non-volatile silicone meaning that it stays on the hair rather than evaporates from it and smoothes the hair like no other thing. Depending on your hair type, it can be a bit difficult to wash out and might cause some build-up (btw, this is not true to all silicones, only the non-volatile types).