If she is moving abroad for full time employment and will be out of the UK for a complete tax year, then it might be possible for her to be non-resident for tax purposes for her entire period abroad. I think the contract needs to be in place before departure though, so if she leaves the UK before finding work in Spain this treatment will not apply.
It is worth bearing in mind that if she leaves the UK during one tax year, and arrives back in the following tax year, it is likely that she will be treated as UK resident for the entire period if she has not been absent from the UK for a complete tax year.
There is further guidance here:
http://www.hmrc.gov.uk/cnr/hmrc6.pdf (Ch 8 will be of most interest to you)
However please note that this document is subject to revision to take into account the changes which came into force on 6 April 2013 - I am unaware of what impact the changes could have on what I have stated above.