The Deputy First Minister also claimed that the Liberal Democrat cabinet minister had "undermined" the pro-union parties' pledge to give Holyrood greater powers if Scotland rejects independence.
"Alistair Carmichael has let the cat out of the bag about Westminster's attitude if there was a No vote," she said.
"Rather than enhanced devolution, there would be a reassertion of Westminster's authority.
"It is not possible to have both, and thanks to Mr Carmichael the UK Government's attitude has now been laid bare."
Earlier this week Mr Carmichael said that maintaining a strong UK Government presence north of the Border after a No vote would ensure the issue of Scotland's future was settled "once and for all".
He also accused Whitehall of allowing the nationalists to "hollow out" the UK Government's profile in Scotland.
The lesson of the independence referendum campaign was that this could never be allowed to happen again, he warned.
LibDem sources insist that the Westminster Government can could maintain a strong profile north of the border at the same time as giving more powers to Holyrood.
Labour, the Lib Dems and the Conservatives have all said that that they will extend powers to Holyrood in the event of a No vote.
But they have all faced calls to publish details about what exactly would be devolved before Scots make their minds up when they go to the polls on September 18.
Mr Carmichael also said that part of the lesson of the referendum was to learn "how we came to be here".
"Part of that process has involved the UK Government not being sufficiently visible in Scotland and we can't allow ourselves to go back to that in the future," he said.
"Whether you do that through somebody called the Scotland Office or some other department, it is not relevant.
"it's the outcome that matters, not the process."
But pro-independence campaigners seized on his comments to suggest that a No vote would ensure that there was no change to how Scotland is governed.
Yes Scotland chief executive Blair Jenkins attacked the Scottish Secretary's comments.
And he claimed that through his argument Mr Carmichael was unwittingly making a "compelling case" for a Yes vote. "The truth is that Westminster isn't working for Scotland," he said.