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Advice required for weed killing

The soil area below my Rhododendron was covered in moss and grass so I gave it a bit of a weed, rake and turned the soil over so is it worth putting down weed killer to stop any further weed and grass growth or will that be bad for the Rhododendron’s ? Also should I add some new top soil ?

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From where you are now, I think a good mulch with garden compost would be best. If deep enough, that would inhibit any weed regrowth.
"Have nothing in your garden that you don't know to be useful, or believe to be beautiful."
Gardening in Central Norfolk on improved gritty moraine over chalk ... free-draining.
Apply after the soil's well moistened though. Anything will do - good compost, leaf mould etc, but bark is also ideal and sets your plants off too.
Weedkiller wouldn't be a good idea, but it also doesn't work if there's nothing for it to act on, so once you remove the weeds it wouldn't do any good anyway.
I live in west central Scotland - not where that photo is...
Weedillers only work on actively growing pants but they have a nasty side effect - poisoning beneficial insects like bees, ladybirds, hoverflies as well as beasties that live below soil, according t articles I've read recently.
I watered thoroughly before adding the mulch , should I water over the top of the mulch now it’s in place or leave it dry ?
A word anti-hoeing. Rhododendrons have VERY shallow roots. You don't want to interfere with those. Mulching should be enough.
Looks like a good job. Well done.
"Have nothing in your garden that you don't know to be useful, or believe to be beautiful."