For a marshmallow cake topping or frosting, you could just use Italian meringue flavored with vanilla. Like any meringue-based item, it will attract moisture from the air and get sticky, so I think that may be what you’ll risk if you allow it to sit around for very long.
Because of the all the butter, vanilla Mousseline doesn’t taste a lot like marshmallow. If you need the stability and longevity of a buttercream and are willing to give up a true marshmallow taste, try the mousseline version with less butter in RHC (Miette’s Tomboy).