You can file MFS electronically with "NRA" listed as the spouse (sometimes, it doesn't always work). However, the IRS doesn't contact you with a form to get her US ITIN. You have to initiate that process.
In order to file Married Filing Jointly you will need to print your tax return and attach Form W-7 to it. You then send the signed W-7 and the required supporting documents to the address in the W-7 instructions (which also outline which supporting documents are required).
The IRS will issue the ITIN and then insert that number on your tax return before forwarding it for processing.
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