No. Your withholdings do not go to the older balance first. If your employer withheld the money from your severance pay in January of 2025, the withholdings will apply to your 2025 taxes.
If you personally made the payment through the IRS site, then you would be able to allocate the payment to go to your 2024 tax year, but since it was withholdings, you cannot do that.
It is similar to people owing back taxes but still working. They apply the amount the employer withholds to what they are currently making not what was owed in the past. If you have a refund due from the IRS they will apply it to past debt.
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