It is possible to qualify for the head of household filing status if you are married and meet the following qualifications:
Per IRS Publication 17 Your Federal Income Tax (For Individuals), page 22, your spouse would need to file as Married Filing Separately:
Married Filing Separately
You can choose married filing separately as your filing status if you are married. This filing status may benefit you if you want to be responsible only for your own tax or if it results in less tax than filing a joint return.
If you and your spouse don't agree to file a joint return, you may have to use this filing status unless you qualify for head of household status.