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“She made an appearance at the request of the White House in which she gave her best understanding of the intelligence that had been provided to her,” Mr. Obama said at a news conference in November. “If Senator McCain and Senator Graham and others want to go after somebody, they should go after me. But for them to go after the U.N. ambassador, who had nothing to do with Benghazi and was simply making a presentation based on intelligence that she had received, and to besmirch her reputation is outrageous.”

Mr. McCain responded to the news of Mrs. Rice’s pending appointment on his Twitter account Wednesday.

“Obviously I disagree w/ POTUS appointment of Susan Rice as Nat’l Security Adviser, but I’ll make every effort to work w/ her on imp’t issues,” he wrote.

Rep. Jason Chaffetz, Utah Republican and a harsh critic of the administration on the Benghazi attacks, wrote on Twitter: “Judgement is key to national security matters. That alone should disqualify Susan Rice from her appointment. #benghazi #BadChoice.”

House Minority Whip Steny H. Hoyer, Maryland Democrat, praised Mrs. Rice for having “led the charge to restore American credibility and influence at the United Nations, in turn improving our national security and effectively protecting the interests of the United States and its allies.”

Charles Stith, a professor at Boston University who served with Mrs. Rice in the Clinton administration, called her “an excellent choice.”

“It keeps one of our most able diplomats involved at one of the most critical junctures in our country’s history,” said Mr. Stith, who was U.S. ambassador to Tanzania. “Her insight into the types of challenges we face in this era of terrorism is as keen as anyone in the foreign policy establishment.”

The appointments of Mrs. Rice and Ms. Power places two women in Mr. Obama’s inner circle after he faced criticism for compiling a nearly all-male leadership team for his second term.

Both women have emphasized human rights as a focus of their work. In spite of that, White House Press Secretary Jay Carney said Mr. Obama will not change his policy toward Syria, where the government of President Bashar Assad has killed tens of thousands of civilians and there has been pressure on Mr. Obama to take a more active role in stopping the slaughter.

The selection of Mrs. Rice for the crucial national-security post is the second time in two days that Mr. Obama has made confrontational moves toward congressional Republicans. On Monday, the president nominated three candidates for vacancies on the D.C. Circuit Court of Appeals, an influential court that some Republican senators are trying to strip of three judgeships.

Ms. Power is a longtime Obama adviser who worked on his 2008 presidential campaign and ran the human rights office in the White House. She left the administration in February, but was considered the favorite to replace Mrs. Rice at the U.N.

She said the question of what the U.N. can accomplish “remains a pressing one.”

“I have seen U.N. aid workers enduring shell fire to deliver food to the people of Sudan, yet I’ve also seen U.N. peacekeepers fail to protect the people of Bosnia,” Ms. Power said. “As the most powerful and inspiring country on this Earth, we have a critical role to play in insisting that the institution meet the necessities of our time. It can do so only with American leadership.”

In March 2008, during the Democratic presidential primary in which Mr. Obama and Mrs. Clinton were competing, Ms. Power said in an interview that Mrs. Clinton “is a monster.”

“She is stooping to anything … if you are poor and she is telling you some story about how Obama is going to take your job away, maybe it will be more effective. The amount of deceit she has put forward is really unattractive,” she said. She later apologized for her remarks and resigned from her unpaid position with the Obama campaign.

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