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You can authorise up to 6 devices at the Sony Ebook library store. One of them must be a computer.
Open the Ebook library software. Go to the Ebook store and navigate to the "my account" option. Then add your wife's device to your account.
However, I see that you are in the UK. If you want to buy books from the Sony Store (formerly called connect) then you will have to claim to live in the USA. And either you will need a US credit card or get someone to buy electronic gift vouchers for you.
If your wife buys a Sony reader in the UK then it will come with a disk for the UK version of the software. Instead of the US Sony store, it goes to Waterstones. She could authorise it there, so as to buy their EPubs.
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