Wife's mother died intestate - separated husband can't be found - complex

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Good morning and thanks in advance for any advice.
Although this may be one for a solicitor.
My wife's mother died 10 years ago and only left some small savings which my wife (thinking she was the only beneficiary) claimed from her bank accounts. This did not cover the funeral costs at the time.
Recently we were sorting some boxes and found two bombshells. First there was evidence of a National Savings account containing £15K and second (more of a bombshell) a wedding certificate from a year before my wife was born.
My wife had no idea that her mother was married and her father left acrimoniously shortly after she was born. He was a Portugese national and went back to Portugal and to my wife's knowledge made no further communications at all.
We have now gone through all of the deceased's papers and found no divorce paperwork so we presume she never divorced (she remained single for the remainder of her life). There is no information at all about her father (other than a name - a common one in Portugal), so we have no clue who he is/was and where he might be. My wife has no living relatives who can shed light on this either.
I understand that letters of administration for the estate need to be obtained to claim amounts of over £5k from National Savings but technically only her missing husband can apply for this. Does anyone know if this is correct? Can my wife apply in place if she declares that her mother's husband cannot be located without unreasonable effort?

My wife's mother died 10 years ago and only left some small savings which my wife (thinking she was the only beneficiary) claimed from her bank accounts. This did not cover the funeral costs at the time.
Recently we were sorting some boxes and found two bombshells. First there was evidence of a National Savings account containing £15K and second (more of a bombshell) a wedding certificate from a year before my wife was born.
My wife had no idea that her mother was married and her father left acrimoniously shortly after she was born. He was a Portugese national and went back to Portugal and to my wife's knowledge made no further communications at all.
We have now gone through all of the deceased's papers and found no divorce paperwork so we presume she never divorced (she remained single for the remainder of her life). There is no information at all about her father (other than a name - a common one in Portugal), so we have no clue who he is/was and where he might be. My wife has no living relatives who can shed light on this either.
I understand that letters of administration for the estate need to be obtained to claim amounts of over £5k from National Savings but technically only her missing husband can apply for this. Does anyone know if this is correct? Can my wife apply in place if she declares that her mother's husband cannot be located without unreasonable effort?
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You wife can apply for probate, but the tricky bit is establishing her marital status at the time of her death as it is quite possible he died before she did. Might be worth ringing the probate office for advice on how to proceed.
Lewis Carroll
The last entry on the accounts was not too far from her date of death and so we think it's likely they are still there, but we will check.
It also seems like a good idea to make an application to NS&I to see what they say at least.